JPH02223433A - Molded matter of metathesis polymer - Google Patents

Abstract

PURPOSE:To obtain favorable surface properties, by a method wherein a metathesis polymerizable monomer is introduced into a mold under the existence of a metathesis polymerizing catalyst and a cured polymeric molded matter having a protrusion whose diameter and width fall within specific ranges to a thickness is molded. CONSTITUTION:A cured polymeric molded matter C to be fitted to a car body of an automobile possesses a protrusion A such as a boss or a rib for fixing a connecting device such as a bolt and nut and obtained by introducing a metathesis polymerizable monomer within a mold under the existence of a metathesis polymerizing catalyst and performing polymerization and molding. With this construction, the protrusion A can be obtained without generating a sink even if the diameter or a width (a) of the protrusion A falls within a range of 1.0T<(a)<=3.5T in relation to a thickness T of the cured polymeric molded matter C. Thus a reduction in weight becomes possible, surface properties are improved and a reduction in molding and finish man-hours can be contrived.

Description

Detailed Description of the Invention: a. Field of Industrial Application The present invention relates to the material and shape of molded articles such as air spoilers used in automobiles that are lightweight and require strength. By using a cured polymer obtained by reaction injection molding of metathesis-polymerizable monomers in the presence of a material for air spoilers, etc., it is possible to create lightweight yet strong air spoilers that have excellent performance using a simple construction method. It is concerned with obtaining shaped articles.

b. Prior Art The following materials have been used for air spoilers, each of which has its own drawbacks and needs to be improved.

■ Injection molding resins such as polypropylene, polyphenylene oxide/nylon copolymer, and polycarbonate/PBT copolymer have good surface properties and are suitable for mass production, but they require a boss structure or strength to attach the air spoiler to the car body. If the rib structure is made larger to provide the air spoiler, sink marks will easily appear on the product surface, and the structure will become complicated to prevent sink marks, and the metal fittings and man-hours required to install the air spoiler will increase, leading to high costs. become.

Furthermore, the mold structure becomes complicated and the cost becomes high.

■ Materials used in SMC, such as unsaturated polyester filled with glass fibers, have excellent physical properties and are cheap in raw material cost, but finishing such as deburring requires a lot of man-hours.

In addition, since it is heavy, it is extremely disadvantageous to the weight reduction required for automobiles.

■ Polyurethane has lower molding pressure than other methods, so the mold cost is low.

However, since it is made of a material that does not comply with the comparative terms and conditions, an iron core etc. is inserted to give it rigidity, making the molding process complicated and increasing costs.

■ Blow molding resins such as polyphenylene oxide, amorphous nylon, and polycarbonate/P B 'I' copolymers are new technologies and are also not widely used.

Although the mold price is low, the surface quality of the molded product is insufficient, and many man-hours for surface finishing etc. are required to meet the quality requirements of the automobile industry.

As a result of intensive research into a molded material that solves these drawbacks, has a simple structure, is easy to install, is lightweight, has excellent performance, has a low mold price, and has low molding and finishing man-hours. This has led to the present invention.

C1 Structure of the Invention The present invention is a cured polymer molded product obtained by introducing a metathesis polymerizable monomer into a mold in the presence of a metathesis polymerization catalyst system, and performing polymerization and molding. Cured polymer moldings having protrusions in the range of diameters or widths indicated.

1.0T<a≦3.5T・[I].

The protrusion is generally called a boss or bolt, and is provided for reinforcing the molded product or for fixing a locking means such as a bolt or nut for attachment to a vehicle body such as an automobile.

As shown in Figure 1, the boss has a cylindrical or semiconical shape, and in the general formula [IJ, a corresponds to the maximum diameter (corresponds to A in Figures 1 and 2). .

The rib has a shape as shown in Figure 2, and has the general formula [IJ
What corresponds to a corresponds to B in FIGS. 3 and 4.

The wall thickness of the cured polymer molded article is the portion corresponding to C in FIGS. 1 to 3 and 4.

The molded product of the present invention has a diameter or rl [a] of its protrusion.
is a≦3.5' for the wall thickness [T] of the molded product! ' condition,
Preferably, the condition of a≦2.5T is satisfied.

In general, when creating a molded product using resin such as polypropylene for injection molding, a>1. If a protrusion with a diameter in the OT range or with an IJ is created, sink marks will occur, making it impossible to create a good molded product. However, the molded product using the metathesis-polymerizable monomer of the present invention can be molded into protrusions with a much larger diameter or rl than with general injection molding resins without generating whiskers or the like. Comparison of moldability between bosses and ribs can be made using the diameter of the boss and the l] of the ribs as a guide. That is, when the diameter of the boss and the rIJ of the rib are the same, the likelihood of sink marks and pinholes occurring is about the same for both. Therefore, the molded product of the present invention can have ribs or bosses that are larger than its wall thickness, and can be used for air spoilers and the like that require light weight and strength.

The air spoiler of the present invention is used for the purpose of rectifying the air flow when a car is running, reducing air resistance, and suppressing the lifting of the car body. Examples include a front spoiler, a rear spoiler, and a rear under spoiler.

The mold or the surface material of the mold can be any material used for molding metathesis polymerizable monomers.

Generally, metal molds such as those made of steel, those with nickel or chrome plating, aluminum (cutting or casting), Kirkside, nickel shell (electroforming or CVD), and a, epoxy resin molds. I can give you things like that. There is no problem even if the materials of the cavity side and core zide are different in one mold.

The mold temperature is generally raised to allow the curing reaction to occur smoothly. In the case of curing using the metathesis polymerization catalyst system in the present invention, the mold temperature is generally 50 to 110'C, especially the temperature of the mold wall on the female mold side is often in the range of 90±10'C. In order to obtain a molded product surface with no depressions on the mold wall surface on the female mold side, it depends on the shape, size, thickness, etc. of the molded product, but generally at least 1.
A temperature difference of 0°C or more, preferably 15 to 50°C is required.

Specific examples of the metathesis polymerizable monomer used in the present invention include dicyclopentadiene, 1-lycyclopentadiene, cyclopentadiene-medylcyclopentadiene codimer, 5-ethylidene norbornene, norbornene 1-norformacyene 5-cyclo xenylnorbornene, 1,4,5.8 dimethanol-1,4,4a, 5.6
, 7,8.8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8.8a octahydronaphthalene, 6-ethylidene-1,458-dimethano-1,4 ,4a,5,7,8.8a-hebutahydro-naphthalene, 1,4,5.8-dimethano-1,4,4a
, 5゜8.8a-hexahythm■7 Naphthalene, ethylene bis(5-norbornene), etc. can be obtained.

In particular, dicyclopentadiene or a mixture containing 50 mol% or more of dicyclopentadiene is preferably used.

Further, if necessary, a metathesis polymerizable monomer having a polar group containing a different element such as oxygen or nitrogen may be used for copolymerization. The copolymerizable monomer 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, a halogen, or the like. Specific examples of such copolymerizable monomers include 5-meth)carbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl 5-
Methylnorbornene, 5-phenylokimethylnorbornene, 5-cyanonorbornene, 6-cyano 1.4,5.
8-dimethano-1,4,4a,5,6,7.8°] 2 8a-octahydronaphthalene, N-butylnadic acid imide, 5-chloronorbornene, and the like.

As mentioned above, the metathesis polymerizable monomer is required to contain as little impurity as possible that would inactivate the metathesis polymerization catalyst system.

The molding method in the present invention may be any molding method as long as it introduces a reactive liquid into a mold, but reaction injection molding is particularly preferred. A method is used in which two solutions, a monomer solution (solution A) and a monomer solution containing an active inhibitor component (solution B), are mixed by collision and then press-fitted into a mold.

Catalyst components in the metathesis polymerization catalyst system for such molding include tungsten and rhenium.

Salts such as halides of metals such as tantalum and molybdenum may be used, but tungsten compounds are particularly preferred6.
- As such a tungsten compound, tanksten halide, tungsten oxyhalide, etc. are preferable6.Also, organic ammonium tanksten hydrochloride, etc. can also be used. When such a tungsten compound is added directly to a monomer, cationic polymerization immediately starts, which is not preferable. Such tungsten compounds can therefore be used in inert solvents such as benzene, toluene.

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

Further, in order to prevent undesirable polymerization as described above, it is preferable to add about 1 to 5 moles of a Lewis base or a chelating agent per mole of the tungsten compound. Such additives include acetylacetone, ace1 to #
Acid alkyl esters.

Examples include tetrahydrofuran and benzonitrile. When using polar monomers, as mentioned above,
It may be itself a Lewis base, and it may have its effect even without the addition of a compound such as those listed in (a) above.

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

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals from Groups 1 to 2 of the periodic table, particularly tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds. Specifically, diethylaluminum chloride,
Examples include ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as active inhibitor components in monomers.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solution A and solution B, but if the above composition remains unchanged, the polymerization reaction will start very quickly, so the molding Hardening may occur before it flows sufficiently into the casting mold, which is often 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, among which ethers, esters, nitriles, etc. are used. Specific examples include edyl benzoate, butyl ether, diglyme, etc. Such regulators are generally added to the solution of the organometallic compound activator component. If 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 to be used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the above 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 activation inhibitor component, the ratio of the aluminum compound to the raw material monomer is about 100:1 to about 2 on a molar basis.
000:1, preferably about 200:1 to about 500:1.

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 may be added to the cured polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers,
Pigments, antioxidants, light stabilizers.

These include flame retardants and polymer modifiers. Such additives cannot be added after the crosslinked polymer of the present invention has been molded, so if they are added, they must be added to the above-mentioned raw material solution in advance.

The easiest method is to use the solution A and solution B.
One method is to add it in advance to either or both of the above, but in that case, it does not react with the highly reactive catalyst component or deactivator component in the liquid to a practical extent, and It must not inhibit polymerization. If the reaction cannot be avoided, or if the reaction does not substantially inhibit polymerization even if the reaction coexists, a third liquid may be prepared by mixing with the monomer, and the third liquid may be mixed and used immediately before polymerization. In addition, 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, It is also possible to fill it.

Additive reinforcements or fillers are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, carphone black, and wollastonite. Those surface-treated with a so-called silane coupler can also be suitably used.

Further, it is preferable that an antioxidant is added 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, tetrakis [methylene (3,5-di-t-butyl-4-droxycinnamate) comethane, etc.] are available.

Furthermore, other polymers can be added to the polymer molded product obtained by the present invention when it is in a monomer solution state.

Such a polymer additive is effective in adding an elastomer to enhance the impact resistance of the molded product and adjusting the viscosity of the 7g liquid. The elastomer used for this purpose is styrene-butadiene-styrene triblock rubber.

Styrene-isoprene-styrene I/riblock rubber,
A wide variety of elastomers can be mentioned, including polybutadiene, polyisoprene, butyl rubber, and ethylene propylene-dientor polymer mononitrile rubber.

In the molding method according to the present invention, once the polymerization reaction starts in the mold, the temperature of the monomer rapidly rises due to the reaction heat.
The polymerization reaction is completed in a short time.

In addition, in the case of metathesis polymerization, double bonds remain in the molded product, and an oxidized layer is formed on the surface.
Adhesion to commonly used paints such as epoxy and polyurethane is good.

d9 Effects of the Invention The molded product of the present invention is lightweight, has a relatively simple structure, has high strength, has a low mold cost, and has low molding and finishing man-hours.6 In particular, it is currently used as a material for air spoilers. It improves the various disadvantages of various materials, and is lightweight, has excellent surface properties and performance, can be manufactured at low cost and with high productivity, and is easy to attach to automobile bodies. It is excellent in certain respects.

e. Examples The present invention will be explained in detail using 61 examples below. Note that the examples are for illustrative purposes only and are not intended to be limiting.

Examples 1-4. Comparative Example 1 [Preparation of catalyst component solution] 720 parts by weight of tank hexachloride was added to 70 parts by volume of dry toluene under a nitrogen stream, and then a solution consisting of 2 parts by weight of nonylphenol and 16 parts by volume of toluene was added. A .5M tungsten-containing catalyst solution was prepared, and this solution was purged with nitrogen scum overnight to remove hydrogen chloride scum generated by the reaction between tungsten hexachloride and nonylphenol, thereby providing a polymerization catalyst.

10 parts by volume of such polymerization catalyst solution, 1 part acedelacetone
500 parts by volume of purified dicyclopentadiene was mixed with 500 parts by volume to make the tungsten content 0. Use solution A of OOIM.

[Preparation of activator component solution] Using 1.lioctylaluminium and dioctylaluminum iodide in a molar ratio of 85:15, mix with purified dicyclopentadiene to obtain 0.00% aluminum.
A 3M solution B was prepared (in addition, the volume part 1 in the above
ml corresponds to 1 g, 11 corresponds to 1 kg) 6 Using such solutions A and B, a metal spray mold is used,
A flat plate with a boss shown in FIG. 2 was created.

The mold temperatures of the female mold side and male mold side are 80℃ and 50℃, respectively.
After injecting the solution into the mold, open the mold 30 seconds later, hold the molded product in the mold for 2 minutes, and then take it out. Thickness of flat plate [T]
Molding is performed using a mold with the size shown in Table 1,
The diameter [a] of the boss, the wall thickness [T] of the flat plate, and the molding state were observed.

Table 1 As can be seen from Table 1, when 4.0T≦a, sink marks or pinholes occur on the boss.

Example 5 A rear spoiler for an automobile having the cross section shown in FIG. 7 was prepared in the same manner as in Examples 1 to 4 using catalyst component solutions and deactivator component solutions prepared in the same manner as in Examples 1 to 4.

The surface of the molded product obtained was extremely beautiful, with no defects such as whiskers or pinholes, and the coated product was sufficiently usable for practical use.

Commercially available rear spoilers made from various materials having the same external shape as the thus obtained rear spoiler.
It is clear that the product of the present invention is superior when comparing the figures. 6 ■ Comparison with an injection-molded resin rear spoiler The boss structure for attaching the rear spoiler to the vehicle body is made as shown in Figure 6, and the product of the present invention is superior. It is more complicated than the invention shown in FIG. 7, and the number of parts and man-hours required for installation are inferior. 6 and 7 show cross sections of the rear spoiler.

Figure 6 shows a passenger car trunk lid steel plate, ■ indicates wall thickness 3.5
+nm injection molding resin, a thin boss like ◎ is provided to prevent whiskers, and a thin lip is attached to reinforce it.
It is fixed with screws and nuts 1-.

On the other hand, since the material of the present invention is extremely unlikely to generate hairs, the rear spoiler and the steel plate can be easily fixed directly with screws and nuts (2) via the thick bosses (2) as shown in FIG.

In FIG. 6, the mold structure is extremely complicated, and the cost is several times higher than that in FIG. 7, which has a simple structure.

■ Comparison with SMCW rear spoiler The rear spoiler of the present invention shown in Fig. 7 has a wall thickness of 3.5 mm, but if an equivalent one was made from SMC, the weight would be approximately 1 mm.
．． This is 8 times as large, which is disadvantageous in meeting the need for weight reduction.

Furthermore, since SMC requires a large mold clamping force, it is not possible to use an inexpensive mold such as a metal spray mold that is simply backed up with resin as in the present invention.

(2) Comparison with a polyurethane rear spoiler For polyurethane obtained by reaction injection molding, the pressure during molding is equivalent to that of the present invention, so an inexpensive mold similar to the present invention can be used.

However, the material of the present invention has a high elastic modulus and has sufficient shape retention on its own like injection molding resin, but polyurethane has an iron core in the rear spoiler to maintain its soft shape. It is molded using advanced molding technology.
The product also becomes heavier.

[Brief explanation of the drawing]

In FIGS. 1 and 2, the molded product has a boss provided on a flat plate. A is the diameter of the boss, and C is the wall thickness of the flat plate. Figures 3 and 4 show 6B, which is a molded product with a lip on a flat plate.
indicates the rlj of the reply. C does not reduce the thickness of the flat plate. FIG. 5 shows an air spoiler. FIG. 6 is a sectional view of a rear spoiler made of a general injection molding resin. ■ indicates a trunk lid of a passenger car, ■ indicates a rear spoiler body, ◎ indicates a boss, and ■ indicates a locking means. FIG. 7 shows a sectional view of the rear spoiler of the present invention. ■ is a trunk lid of a passenger car, ■ is a boss, and ■ is a locking means. diagram diagram

Claims (1)

[Scope of Claims] 1. A cured polymer molded product obtained by introducing a metathesis polymerizable monomer into a mold in the presence of a metathesis polymerization catalyst system, polymerizing and molding, and having the following general formula [
A cured polymer molded article having a protrusion having a diameter or width within the range represented by I. 1.0T<a≦3.5T... [I] [In the formula, T represents the wall thickness of the molded product after curing and polymerization. a represents the diameter or width of the protrusion. 2. The cured polymer molded article according to claim 1, wherein the cured polymer molded article is an air spoiler. 3. The molding method according to any one of claims 1 to 2, in which the molding is performed by a reaction injection molding method. 4. The molded article 5, according to any one of claims 1 to 2, in which the molding is performed by a premix method. 5. Any one of claims 1 to 4, wherein the mold is made of steel, copper, aluminum, kirksite, nickel, tin, or epoxy resin, or a mold made of steel or copper whose surface is plated with nickel or chromium. The molded article 6 according to claim 1, wherein the metathesis polymerization catalyst system comprises a metathesis polymerization catalyst component and an activator component. 7. The reactive liquid consists of two liquids: a liquid containing a metathesis polymerizable monomer and a metathesis polymerization catalyst component, and a liquid containing a metathesis polymerizable monomer and an activator component,
The molded article 8 according to claim 3 or 6, wherein the reaction injection molding is carried out while collision-mixing the two liquids, wherein the metathesis polymerization catalyst component consists of at least one halide of metal selected from tungsten, rhenium, tantalum, and molybdenum. The molded article according to claim 6. 9. Molded article according to claim 8, wherein the metathesis polymerization catalyst component is at least one selected from tungsten halide and tungsten oxyhalide. 10. The metathesis polymerization catalyst component is at least one selected from tungsten hexachloride and tungsten oxychloride The method according to claim 9, wherein the method is one type. 11. The molded article according to claim 6, wherein the activator component is an alkylated product of a metal belonging to Groups I to III of the Periodic Table. 12. The molded article according to claim 11, wherein the activator component is at least one selected from tetraalkyl tin, alkyl aluminum compounds, and alkyl aluminum halide compounds. 13. The method according to claim 1, wherein the reactive liquid contains a catalyst activity modifier. 14. Claim 13 wherein the catalyst activity regulator is a Lewis base.
The molded article described. 15. The metathesis polymerizable monomer is dicyclopentadiene, tricyclopentadiene, cyclopentadiene-
Methylcyclopentadiene codimer, 5-ethylidenenorbornene, norbornene, norbornadiene, 5-cyclohexenylnorbornene, 1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octa Hydronaphthalene, 1,4-methano-1,4,4a,5,6
, 7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,
7,8,8a-heptahydro-naphthalene, 1,4,5
, 8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, and ethylenebis(5-norbornene). 16. The molded article according to claim 15, wherein the metathesis polymerizable monomer is dicyclopentadiene. 17. The metathesis polymerizable monomer is dicyclopentadiene, tricyclopentadiene, cyclopentadiene-
Methylcyclopentadiene codimer, 5-ethylidenenorbornene, norbornene, norbornadiene, 5-cyclohexenylnorbornene, 1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octa Hydronaphthalene, 1,4-methano-1,4,4a,5,6
, 7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,
7,8,8a-heptahydro-naphthalene, 1,4,5
, 8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, and ethylenebis(5-norbornene), and different species such as oxygen, nitrogen, and sulfur. The molded article according to claim 1, comprising at least one metathesis-polymerizable monomer having a polar group containing an element. 18. The molded article according to claim 17, wherein the metathesis polymerizable monomer comprises dicyclopentadiene and at least one metathesis polymerizable monomer having a polar group containing a different element such as oxygen, nitrogen, or sulfur. 19. The molded article according to claim 1, wherein the reactive liquid contains at least one of a filler, a pigment, an antioxidant, a light stabilizer, a flame retardant, and a polymer modifier.