JPH05262857A - Production of norbornene resin molding - Google Patents

Abstract

PURPOSE:To produce industrially advantageously the title molding having good physical properties and emitting little odor by reusing waste of the molding. CONSTITUTION:A reaction soln. contg. a norbornene monomer and a metathesis cocatalyst is mixed with a reaction soln. which contains an active metathesis catalyst and comprises the monomer and a powdered norbornene resin molding swelled by the monomer. The resulting mixture is bulk polymerized in a mold. Flashes, gates, rejected parts, etc., formed in the molding step are thus mixed into the molding material and reused in the same production process, and the material balance can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for bulk-polymerizing norbornene-based monomers in a mold to produce a resin molded product.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of protecting the global environment, there has been a great demand for recovering resin molded products to reuse them in resin molding materials and other applications. A norbornene-based monomer represented by dicyclopentadiene (DCP) is formed in a mold by reaction injection molding (RI
The norbornene-based resin molded product obtained by M) is generally a thermosetting type, and it is difficult to reuse it as a resin molding material as compared with a thermoplastic resin molded product.

Generally, as a method for recycling vulcanized rubber, urethane foam, cross-linked polyethylene, and fiber reinforced thermosetting resin (FRP) molded products, they can be reused in other forms in the same shape, or made into chips or fine powder. It is known to mix it with a fresh resin molding material as a filler and reuse it. For example, in the case of a tire, the tire is used as it is, for example, as a playground equipment, a cushioning material, and the like, in applications other than the tire. Further, in the case of urethane foam, it is made into chips and mixed with a urethane resin molding material and reused as a foam. In the case of FRP, it is finely pulverized and mixed into a fresh FRP molding material or concrete material as a filler to be reused.

In the case of a norbornene-based resin molded product obtained by reaction injection molding, a recycling method similar to the above-mentioned other thermosetting resin molded products can be considered. For example, a method of compression-molding by adding a crosslinking agent after pulverizing, and
For example, a method of mixing as a filler into another resin molding material such as a thermoplastic resin or unsaturated polyester can be considered.

All of the above-mentioned reuse methods are used for purposes other than the original purpose of the resin molded product before recycling, but it is difficult to secure the quality such as physical properties and appearance in the recycling application. That is, it is difficult to maintain a constant quantitative balance between the amount of reusable molded products produced and the amount of waste generated, and there is no reuse destination for molded products of the same product or the same material. However, there is a problem in that burrs, gates, defective products, etc., which are generated in 1) cannot be effectively used by being mixed with the resin molding material in the same molding product manufacturing process. It is strongly required to reuse the waste generated in the molding process in the same process from the viewpoint of mass balance and economical rationality such as labor for transfer and storage.

[0006]

As a result of investigating the reuse of norbornene-based resin molded products as resin molding materials, the inventors have found that the metathesis catalyst component remaining in the norbornene-based resin molded products is We obtained the finding that the polymerization activity is retained even after a lapse of time and after the pulverization step, and based on this finding, the activity of the metathesis catalyst remaining in the norbornene-based resin molded product to be discarded The method for producing a norbornene-based resin molded product of the present invention in which the above is reused has been completed. Therefore, an object of the present invention is to provide a method for industrially producing a norbornene-based resin molded product having good physical properties by reusing the waste of the norbornene-based resin molded product.

The molded article obtained by the production method of the present invention is
Compared to a molded product obtained from a norbornene-based monomer without blending a crushed product of a norbornene-based resin molded product, it has physical properties comparable to those of a molded product and has little odor. Further, in the manufacturing method of the present invention, the crushed product of the norbornene-based resin molded product is mixed with the norbornene-based monomer to be reused, so that burrs, gates, defective products and the like generated in the molding process can be used in the same molded product manufacturing process. Since it can be reused by mixing it with the molding material, it is easy to obtain a material balance. Further, the resin molded product obtained by the production method of the present invention can be crushed at the time of disposal and blended again with the norbornene-based monomer to be used as a molding raw material.

[0008]

Means for Solving the Problems The present invention provides a reaction liquid (A liquid) containing a norbornene-based monomer and a metathesis cocatalyst.
And a crushed product of a norbornene-based resin molded product containing an active metathesis catalyst are mixed with a norbornene-based monomer and swollen with the reaction liquid (solution B), and the mixture is subjected to bulk polymerization in a mold. A method for producing a norbornene-based resin molded article is provided.

The method for producing the norbornene-based resin molded product of the present invention will be described in detail below. In the production method of the present invention,
The thermosetting norbornene-based resin molded product to be reused is a molded product obtained by bulk-polymerizing a norbornene-based monomer in a mold using a metathesis catalyst. This resin molded product is reused in the form of a crushed product. The pulverized product is obtained by, for example, cutting into chips by using a pelletizer, a grinder, a cutter or the like, and then finely pulverizing it using a ball mill, a jet mill, a pulverizer or the like. The pulverization can be carried out in air, but it is preferably carried out in nitrogen or other inert gas in consideration of the risk of dust explosion.

It is preferable that the pulverized product is a powder having a particle size of 500 μm or less. More preferable powder particle size is 20
It is 0 micron or less, more preferably 100 micron or less. It is preferable that the pulverized product is composed of a powder which is as small as possible so that the physical properties of the molded product after reuse are good. Therefore, it is desirable to make the particle size as small as possible in consideration of the economical efficiency of the pulverization process.

The catalyst remaining in the thermosetting norbornene-based resin molded product to be reused is a metathesis catalyst, and is not particularly limited as long as the activity is maintained. Examples of the metathesis catalyst include halides such as tungsten, molybdenum, and tantalum, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyacid salts. Among them, particularly for water and oxygen. Oxyhalogen compounds such as stable and stable organic ammonium salts of tungsten and molybdenum and phenoxylated halogen compounds are preferred.

In order to perform bulk polymerization of a norbornene-based monomer in a mold using a crushed product of a norbornene-based resin molded product containing an active metathesis catalyst, the crushed product is blended with a norbornene-based monomer and swollen with the monomer. The reaction solution (B solution) thus prepared and a reaction solution (A solution) containing a norbornene-based monomer and a metathesis cocatalyst are prepared, both reaction solutions are mixed, and this mixed solution is bulk polymerized in a mold.

When the crushed product of the norbornene-based resin molded product is mixed with the norbornene-based monomer and allowed to swell, the viscosity of the mixed solution at the beginning of mixing the crushed product is at least 2 times or more, or even 5 times or more. It is preferable to swell.
Generally, to increase the viscosity of the mixture to this extent, 2
Approximately 20 hours or more at room temperature of 0 ° C, and about 5 at 35 ° C.
Stir for more than an hour. The swelling degree is preferably as high as possible, and it is important that the liquid B does not contain impurities such as oxygen and water. Therefore, it is preferable that after swelling, the liquid B is degassed under reduced pressure, returned to a nitrogen atmosphere, and stored.

In the preparation of the liquid B, the blended amount of the crushed norbornene resin molded product is preferably in the range of 1 to 50% by weight, particularly 5 to 30% by weight based on the weight of the liquid B. If the blended amount of the pulverized product is too large, the viscosity of the blended liquid increases, which makes handling difficult. Addition of new catalyst to solution B is not essential. When a catalyst is added, the smoke time at 30 ° C. (refers to the time from the start of the mixing of the liquids A and B until the slight smoke is generated from the surface of the produced polymer).
Keep it within 5 minutes. When a large amount of the catalyst is added, the reactivity becomes high, and the polymerization occurs before the cocatalyst component enters the voids of the pulverized material. As a result, unreacted monomer remains inside the pulverized product, which causes odor and also leads to deterioration of physical properties.

The liquid B and the reaction liquid (liquid A) containing the metathesis cocatalyst and the norbornene-based monomer are both stored and manipulated in an atmosphere of an inert gas such as nitrogen gas. It is preferable to mix the liquid A and the liquid B at room temperature. If the mixing temperature is high, the reaction will start immediately after mixing,
The viscosity of the liquid increases and it becomes difficult to inject it into the mold.

Immediately after mixing the solutions A and B, the mixed solution is poured into the mold to start the polymerization. Since the activity of the catalyst system of the mixed solution is suppressed, the mold temperature is preferably 70 ° C. or higher, particularly 80 ° C. or higher in order to accelerate the polymerization and sufficiently cure in a relatively short time. The bulk polymerization of the mixed solution can be carried out by the same method under the same conditions as in a usual reaction system in which a pulverized resin is not mixed.

In order to carry out the bulk polymerization in the mold, a collision mixing device known as a reaction injection molding (RIM) device can be used for mixing the liquid A and the liquid B. That is, the flows of the reaction liquids from the separate containers containing the liquid A and the liquid B are mixed instantaneously by the mixing head of the RIM device, and then injected into the mold kept at a high temperature.
Alternatively, liquid A and liquid B may be mixed in a mixer, and the mixed liquid may be injected and injected into a mold several times (for example, JP-A-59-51911 and US Pat. No. 4,426,502).
No.), or may be continuously injected.

As the norbornene-based monomer, a cycloolefin having a norbornene group is used. A bicyclic or tricyclic or more polycyclic norbornene is used as such a cycloolefin, and specific examples thereof include:
Norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorinated norbornene, chloromethylnorbornene, trimethylsilylated norbornene, phenylnorbornene, cyanonorbornene, dicyanonorbornene, methoxycarbonylnorbornene, pyridylnorbornene, nadic acid anhydride, nadic acid imide, etc. Tricyclic norbornenes such as bicyclic norbornene, dicyclopentadiene, dihydrocyclopentadiene and their alkyl, alkenyl, alkylidene and aryl substitution products, dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and their alkyl, alkenyl, alkylidene and aryl substitution products Tetracyclic norbornene such as, pentacyclic norbornene such as tricyclopentadiene, hex Such as six ring norbornene, such as cyclo hepta-decene, and the like. Also, dinorbornene,
Examples thereof include a compound in which two norbornene rings are linked by a hydrocarbon chain or an ester group, and a compound containing a norbornene ring such as an alkyl or aryl substitution product thereof. The above norbornene-based monomers may be used alone or in combination of two or more, but it is preferable to use two or more kinds. When two or more kinds are used, various properties can be obtained by appropriately combining a monomer having one double bond which is a thermoplastic resin and a monomer having a plurality of double bonds which is a thermosetting resin. Resin is available.

Examples of the cocatalyst used for preparing the liquid A include organometallic compounds which have a function of reducing the metathesis catalyst used in the bulk polymerization of norbornene-based monomers. Examples thereof include organic aluminum compounds such as alkylaluminum, alkylaluminum halides, alkoxyalkylaluminum halides and aryloxyalkylaluminum halides, organic tin compounds, organic zinc compounds, organic magnesium compounds, and organic silane compounds.

The liquid A may contain an activator in addition to the organometallic compound having a reducing action. As the activator, halogenated alcohol, halogenated ketone, halogenated ester, metal alkoxide, metal halide,
There are halogenated hydrocarbons. Particularly preferred cocatalysts are those which exhibit high activity at low concentrations, such as the combination of dimethyl aluminum chloride and halogenated alcohols. Specific examples of the halogenated alcohol include 1-chloro-2-ethanol, 1,1-dichloro-2-ethanol, 1,1,1-trichloro-2-ethanol, 1-
Chloro-2-propanol, 1,3-dichloro-2-propanol, 1,1-dichloro-2-propanol,
1,1,1-trichloro-2-propanol, hexachloroisopropanol, 2-chloro-2-propene-1
-Ol, 1-chloro-2-butanol, 1-chloro-
3-methoxy-2-propanol, 1,3-dibromo-
2-propanol, 1,3-diiodo-2-propanol, 2-chlorocyclohexanol and the like can be mentioned.

As described above, as the metathesis catalyst which may be optionally added in the preparation of the liquid B, an organic ammonium salt of tungsten and molybdenum and an oxyhalogen compound such as a phenoxy halogen compound are preferably used. Specific examples of preferred metathesis catalysts include tridodecyl ammonium molybdate and tungstate, methyl tricapryl ammonium molybdate and tungstate, tri (tridecyl) ammonium molybdate and tungstate, and trioctyl ammonium molybdenum. Examples thereof include acid salts and tungstates.

The amount of the metathesis catalyst to be used is usually 0.01 with respect to 1 mol of the norbornene-based monomer as the total amount of the catalyst contained in the pulverized norbornene-based resin and the catalyst which may be newly added if desired. It is used in the range of .about.50 mmol, preferably 0.05 to 5 mmol.
Generally, the amount of newly added metathesis catalyst is 30 ° C.
It suffices that the smoke time in 5 is not less than 5 minutes. The cocatalyst is usually 0.1 to 2 with respect to the catalyst component.
It is used in the range of 00 (molar ratio), preferably 1 to 10 (molar ratio).

Various additives may be added to either one or both of the liquids A and B, depending on the desired properties of the resulting molded product. As an additive, phenol-based,
Phosphorus and amine antioxidants, UV absorbers, elastomers, polymer modifiers, glass powder, carbon black, talc, calcium carbonate, mica, fillers such as aluminum hydroxide, colorants, flame retardants , Crosslinking agents, sliding agents, odorants, lightweight fillers, foaming agents, surface smoothing whiskers, and the like.

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Also, the parts and% in these examples
Is weight basis unless otherwise specified. Reference Example 1 Styrene-isoprene-styrene block copolymer (manufactured by Nippon Zeon Co., Ltd., trade name Quintac 3421) in a monomer mixture consisting of 90 parts of dicyclopentadiene (DCP) and 10 parts of tricyclopentadiene (TCP).
5 parts and polybutadiene (manufactured by Nippon Zeon Co., Ltd., trade name 1
220) 1.0 part was added and mixed into two containers, and one container contained diethylaluminum chloride (DEAC) in a concentration of 41 mmol and 1,3-dichloro-2-propanol in one container. (DCPr)
Were added so that the concentration would be 41 mmol (original reaction solution A). To the other container, tri (decyl) ammonium molybdate was added to the monomer so as to have a concentration of 10 mmol, and further, a phenolic antioxidant (manufactured by Ethyl Corporation, trade name Etanox 7).
02) 4 parts was added (raw reaction solution B). Both reaction stock solutions A and B were mixed at a ratio of 1: 1 (weight ratio) using a gear pump and a power mixer, and then poured into a mold having an open upper cavity maintained at 70 ° C.
A mm square flat plate was formed.

Glass transition temperature (Tg) of the obtained molded plate
Was measured by a differential scanning calorimeter (DSC) to find 15
It was 2 ° C. Further, the conversion rate of the residual ratio of the weight of the polymer when heated from room temperature to 400 ° C. by a thermobalance was 98%. Further, the bending strength and bending elastic modulus (both measured at 23 ° C.) and impact strength (Izod impact value, notched, measured at 23 ° C.) were measured. The results are shown in Table 1. Almost no odor of the molded plate was observed. Next, the flat plate was crushed to a size of about 2 mm with a sheet pelletizer (manufactured by Tomoki Iron Works Co., Ltd.), then pulverized to a size of 500 microns or less by a pulsarizer (manufactured by Tokyo Atomizer), and further a jet mill (manufactured by Fuji Sangyo).
Was pulverized to a size of 100 microns or less in a nitrogen atmosphere to obtain a pulverized product.

[0026] The DCP90 parts of ground product 20 parts obtained in Reference Example 1 in the monomer mixture 100 parts of the TCP10 parts of Example 1 Viscosity 10 centipoise (25 ° C.) were mixed at room temperature, phenol was left 24 hours 4 parts of an antioxidant (Ethanox 702) was added, the mixture was exposed to reduced pressure at 40 ° C. for 30 minutes, and then returned to normal pressure and 23 ° C. in a nitrogen atmosphere to obtain a reaction stock solution (solution B).
The viscosity of this liquid B was 300 centipoise (23 ° C.).

This solution B (23 ° C.) and the original reaction solution A (23 ° C.) prepared in Reference Example 1 were mixed at a ratio of 1: 1 using a gear pump and a power mixer, and then a mold maintained at 90 ° C. It was poured into the inside and a 200 mm square flat plate having a thickness of 4 mm was formed. The injection time was 15 seconds. Smoke was observed about 1 minute after the injection into the mold, and 5 minutes after that, the molded plate was taken out from the mold. The Tg of the obtained molded plate was 106 ° C. The conversion rate was 82%. This result is
It is shown that polymerization is performed even if a new catalyst is not added to the liquid B.

Example 2 A molding was carried out in the same manner as in Example 1 except that tri (tridecyl) ammonium molybdate was added in advance to the monomer so as to have a concentration of 4 mm when the solution B was prepared in Example 1. The plate was molded. Table 1 shows the physical properties of the obtained molded plate. Almost no odor of the molded plate was observed as in Reference Example 1. In addition, the original reaction solution A and solution B were mixed at room temperature, and the smoke time was about 20 minutes when left alone.

In Examples 3 and 4, the same as Example 2 except that the addition amount of the pulverized product obtained in Reference Example 1 used in the preparation of solution B was changed as shown in Table 1. A molded plate was molded. Table 1 shows the physical properties of the obtained molded plate.

[0030]

[Table 1]

[0031]

EFFECTS OF THE INVENTION By recycling the discarded crushed norbornene-based resin molded product as a molding raw material according to the method of the present invention, the active metathesis catalyst contained in the molded product is effectively utilized and good physical properties are obtained. It is possible to industrially produce a molded product having As shown in the above Examples, the molded product obtained by the production method of the present invention is almost comparable to the molded product obtained from the norbornene-based monomer without blending the crushed product of the norbornene-based resin molded product. It has physical properties and has little odor. Further, in the manufacturing method of the present invention, the crushed product of the norbornene-based resin molded product is mixed with the norbornene-based monomer to be reused, so that burrs, gates, defective products and the like generated in the molding process can be used in the same molded product manufacturing process. Since it can be reused by mixing it with the molding material, it is easy to obtain a material balance. Further, the resin molded product obtained by the production method of the present invention can be crushed at the time of disposal and blended again with the norbornene-based monomer to be used as a molding raw material.

Claims (2)

[Claims] 1. A reaction liquid (Liquid A) containing a norbornene-based monomer and a metathesis cocatalyst, and a crushed product of a norbornene-based resin molded product containing an active metathesis catalyst are mixed with the norbornene-based monomer and swollen with the monomer. A method for producing a norbornene-based resin molded article, which comprises mixing the reaction liquid (Liquid B) and bulk polymerizing the mixture in a mold. 2. The method for producing a norbornene-based resin molded article according to claim 1, wherein the metathesis catalyst is added to solution B in an amount such that the smoke time at 30 ° C. does not become 5 minutes or less.