JP3116536B2 - Production method for norbornene resin molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin molded product by bulk polymerization of a norbornene-based monomer in a mold.

[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 and reusing them in resin molding materials and other uses. Reaction injection molding (RI) of a norbornene monomer represented by dicyclopentadiene (DCP) in a mold
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.

[0003] Generally, as a method of recycling vulcanized rubber, urethane foam, crosslinked polyethylene, and fiber reinforced thermosetting resin (FRP) molded products, they can be reused as they are for other uses, or formed into chips or pulverized. It is known that the resin is mixed with fresh resin molding material as a filler and reused. For example, in the case of a tire, for example, it is used as it is in a form other than a tire as a playground equipment, a cushioning material or the like. Further, in the case of urethane foam, it is chipped and mixed with a urethane resin molding material and reused as a foam. In the case of FRP, it is pulverized, mixed into a fresh FRP molding material, concrete material, or the like as a filler and reused.

[0004] In the case of norbornene-based resin molded products obtained by reaction injection molding, the same recycling method as the above-mentioned other thermosetting resin molded products can be considered. For example, after pulverized, a method of compression molding by adding a crosslinking agent, 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.

[0005] In any of the above-mentioned recycling methods, the resin molded product before recycling is reused for uses other than the intended use, but it is difficult to ensure the properties such as physical properties and appearance in the recycle use. In addition, it is difficult to maintain a constant quantitative balance between the production of reused molded products and the amount of waste generated, and there is no place to reuse the same product or the same material for molded products. There is a problem that burrs, gates, defective products, and the like generated in the above are mixed into the resin molding material in the same molded product manufacturing process and cannot be used effectively. It is strongly demanded that the waste generated in the molding process be reused in the same process from the viewpoint of material balance and economic rationality such as labor for transport and storage.

[0006] There has been no attempt to recycle a norbornene-based resin into a powder by pulverizing the norbornene-based resin molded product, adding the powder to a norbornene-based monomer as a filler, and reusing the norbornene-based resin for molding. This is because the surface of the norbornene-based resin molded product is easily oxidized, and the powder obtained by pulverizing the molded product is considered to be more easily oxidized. This is because it is predicted that if this is mixed with the polymerization raw material, polymerization inhibition will occur.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have studied the reuse of norbornene-based resin molded products as resin molding materials. As a result, the powder obtained by pulverizing the norbornene-based resin molded products was used as norbornene-based resin. Surprisingly, the blended liquid obtained by blending with the system monomer does not decrease the activity of the catalyst system due to the reduction of the resin pulverized product, and it becomes a good norbornene resin molded product by bulk polymerization with a metathesis catalyst. I found it. Therefore, an object of the present invention is to provide a method for industrially and advantageously producing norbornene-based resin molded products having good physical properties by recycling wastes of norbornene-based resin molded products.

[0008] The molded article obtained by the production method of the present invention comprises:
It has almost the same physical properties as a molded product obtained from a norbornene-based monomer without incorporating a pulverized norbornene-based resin molded product, and has a low odor. Furthermore, in the production method of the present invention, the crushed norbornene-based resin molded product is mixed with the norbornene-based monomer and reused. Since it can be mixed with the molding material and reused, it is easy to obtain a material balance. Further, the resin molded product obtained by the production method of the present invention can be pulverized at the time of disposal, blended with the norbornene-based monomer again, and used as a raw material for molding.

[0009]

According to the present invention, there is provided a method for mass-polymerizing a norbornene-based monomer in a mold using a metathesis catalyst in the presence of a powder obtained by grinding a thermoset norbornene-based resin molded product. And a method for producing a norbornene-based resin molded product.

Hereinafter, the method for producing the norbornene-based resin molded product of the present invention will be described in detail. In the production method of the present invention,
A thermosetting norbornene-based resin molded article to be reused (hereinafter simply referred to as "norbornene-based resin molded article") is obtained by bulk polymerization of a norbornene-based monomer in a mold using a metathesis catalyst. It is a molded product. This resin molded product is pulverized and reused in the form of powder. The powder is obtained by, for example, chopping with a pelletizer, a grinder, a cutter, or the like into chips, and then pulverizing the powder using a ball mill, a jet mill, a pulverizer, or the like. The pulverization can be performed in the air, but is preferably performed in nitrogen or other inert gas in consideration of the risk of dust explosion.

The pulverized product is preferably composed of a powder having a particle size of 500 microns or less. A more preferred powder particle size is 20.
0 μm or less, more preferably 100 μm or less. The pulverized material made of a powder as small as possible has better physical properties of the molded product after reuse. Therefore, it is desirable to reduce the particle size as much as possible in consideration of the economics of the pulverization step. However, if the particle size is excessively small, there is a problem that the mixture swells rapidly when mixed with the monomer.

The catalyst remaining in the norbornene resin molded article to be reused is a metathesis catalyst. Examples of metathesis catalysts include tungsten, molybdenum,
Halides such as tantalum, oxyhalides, oxides, organic ammonium salts, oxyacid salts, heteropolyacid salts and the like, among which water and oxygen-stable organic ammonium salts of tungsten and molybdenum and Oxyhalogen compounds such as phenoxylated halogen compounds are preferred.

In order to perform bulk polymerization of a norbornene-based monomer in a mold using the powder of a norbornene-based resin molded product, a reaction stock solution obtained by mixing the powder and a metathesis cocatalyst with the norbornene-based monomer is used. It is preferable to mix a substantially non-swelled state (Solution B) and a reaction stock solution (Solution A) containing a norbornene-based monomer and a metathesis cocatalyst, and to carry out bulk polymerization of the mixture in a mold.

[0014] The condition that the pulverized norbornene resin molded product is in a substantially non-swelling state means that the viscosity of the initial liquid mixture obtained by mixing the pulverized thermosetting norbornene resin and the monomer does not reach twice. Say that there is. The viscosity of the liquid B when mixed with the liquid A is preferably 1.5 times or less the viscosity of the initially mixed liquid obtained by mixing the pulverized product and the monomer. A
In order to make the viscosity of the liquid B less than twice the initial viscosity when mixing the liquid and the liquid B, the liquid B is, for example, within about 15 hours at room temperature of 20 ° C., preferably within 5 hours, and about 35 ° C. The solution A may be mixed within 4 hours, preferably within 3 hours.

The reason for mixing with the liquid A while the pulverized material in the liquid B is in a substantially non-swelled state is based on the following reason. The resin pulverized material is swollen in the liquid B, and the monomer is permeated into the gaps between the pulverized material particles, mixed with the liquid A, and reacted at a high reaction rate. Before the cocatalyst is sufficiently diffused, curing proceeds on the peripheral surface of the pulverized product particles, so that unreacted monomers remain in the gaps between the particles, resulting in reduced physical properties of the resulting molded article and odor from the molded article. Occur.

Since the active metathesis catalyst remains in the pulverized product of the norbornene resin molded product, the pulverized product cannot be mixed with the liquid A containing the cocatalyst. When mixed with the liquid A, the reaction gradually proceeds and the viscosity of the liquid increases. The compounding amount of the pulverized resin molded product in the liquid B is preferably 1 to 60% by weight, particularly preferably 5 to 40% by weight, based on the weight of the liquid B. If the blending amount is too large, the viscosity of the blended liquid increases, and handling becomes difficult.

The pulverized norbornene resin molded product is B
Prior to preparing the liquid, it is preferable to treat it with a high-boiling inert oil. When treated with a high-boiling inert oil, the gaps between the pulverized material particles are closed with the inert oil, and the permeation of the monomer is prevented. Therefore, the amount of residual unreacted monomer in the obtained molded article can be significantly reduced, and odor is completely eliminated. As the high boiling point inert oil, hydrocarbon oils having a boiling point of 180 ° C. or higher and halogenated hydrocarbon oils are preferable. Specific examples include paraffin oil, naphthenic oil, aroma oil,
Chlorinated paraffin and the like can be mentioned.

The solution B and the reaction solution (solution A) containing the metathesis cocatalyst and the norbornene-based monomer are both stored and operated in an atmosphere of an inert gas such as nitrogen gas. The mixing of the solution A and the solution B is preferably performed at room temperature. If the mixing temperature is high, the reaction starts immediately after mixing,
The viscosity of the liquid increases, making it difficult to pour the liquid into the mold.

Immediately after mixing the liquid A and the liquid B, the mixed liquid is poured into a mold to start polymerization. Since the activity of the catalyst system of the mixed solution is suppressed, the mold temperature is preferably 70 ° C. or more, particularly preferably 80 ° C. or more, in order to promote 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 normal reaction system in which no pulverized resin is mixed.

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

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

As a catalyst used for preparing the solution B, a metathesis catalyst known as a catalyst for ring-opening polymerization of norbornene monomers (for example, Japanese Patent Application No. 58-127728,
No. 58-129013) is used, and there is no particular limitation. Examples of metathesis catalysts include:
Tungsten, molybdenum, halides such as tantalum, oxyhalides, oxides, organic ammonium salts, oxyacid salts, heteropolyacid salts, etc., among them, especially water and oxygen stable tungsten and molybdenum organic Oxyhalogen compounds such as ammonium salts and phenoxylated halogen compounds are preferred. Specific examples of preferred metathesis catalysts include tridodecyl ammonium molybdate and tungstate, methyl tricaprylammonium molybdate and tungstate, tri- (tridecyl) ammonium molybdate and tungstate, and trioctylammonium molybdenum. Acid salts and tungsten hydrochloride.

The amounts of the metathesis catalyst used are solution A and solution B
It is used in an amount of usually 0.01 to 50 mmol, preferably 0.05 to 5 mmol, per 1 mol of the norbornene-based monomer in the liquid. The cocatalyst is used in an amount of usually 0.1 to 200 (molar ratio), preferably 1 to 1 (molar ratio), based on the amount of the catalyst component.
It is used in the range of 0 (molar ratio).

Examples of the cocatalyst used for preparing the solution A include organometallic compounds having an action of reducing a metathesis catalyst conventionally used in bulk polymerization of norbornene monomers. Examples thereof include organoaluminum compounds such as alkylaluminum, alkylaluminum halide, alkoxyalkylaluminum halide and aryloxyalkylaluminum halide, organotin compounds, organozinc compounds, organomagnesium compounds, and organosilane compounds.

In the solution A, an activator can be used in addition to the organometallic compound having a reducing action. Activators include halogenated alcohols, halogenated ketones, halogenated esters, metal alkoxides, metal halides,
And halogenated hydrocarbons. Particularly preferred cocatalysts are those that exhibit high activity at low concentrations, such as the combination of dimethyl aluminum chloride and a halogenated alcohol. Specific examples of the halogenated alcohol include 1-chloro-2-ethanol, 1,1-dichloro-2-ethanol, 1,1,1-trichloro-2-ethanol, and 1-chloro-2-ethanol.
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.

As the metathesis catalyst which may be added as needed in the preparation of the solution B, as described above, organic ammonium salts of tungsten and molybdenum and oxyhalogen compounds such as phenoxylated halogen compounds are preferably used. Specific examples of preferred metathesis catalysts include tridodecylammonium molybdate and tungstate, methyltricaprylammonium molybdate and tungstate, tri (tridecyl) ammonium molybdate and tungstate, and trioctylammonium molybdenum And tungstates.

If desired, a crosslinking agent such as sulfur or peroxide and a vulcanization accelerator thereof can be added to the solution B. When these are added, the heat resistance of the molded article is improved, and generation of odor is more completely prevented. The addition amount is preferably equal to or less than that of the pulverized resin molded product. In particular, when the molded product is a thick product, the effect of the crosslinking agent is remarkable. That is, the resin temperature is 150 to 250 ° C. during molding, but in the case of a thick molded product, the maintenance time at this temperature is long, so that crosslinking is easy, heat resistance is improved, and generation of odor is suppressed. Is done.
After the molding in the mold is completed, it can be removed from the mold and subjected to an aging reaction in a heating furnace or the like.

Various additives can be added to one or both of the solution A and the solution B depending on the desired properties of the obtained molded article. Phenolic,
Phosphorus and amine antioxidants, UV absorbers, elastomers, polymer modifiers, glass powder, fillers such as carbon black, talc, calcium carbonate, mica, aluminum hydroxide, coloring agents, flame retardants , A cross-linking agent, a sliding agent, an odorant, fillers for reducing weight, a foaming agent, whiskers for smoothing the surface, and the like.

[0029]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples. Also, the parts and percentages in these examples
Are by weight unless otherwise specified. Reference Example 1 A styrene-isoprene-styrene block copolymer (manufactured by Zeon Corporation, trade name Quintac 3421) was added to a monomer mixture consisting of 90 parts of dicyclopentadiene (DCP) and 10 parts of tricyclopentadiene (TCP).
5 parts and polybutadiene (Nippon Zeon Co., Ltd., trade name 1
220) A mixture containing 1.0 part of the mixture was placed in two containers, and one container contained 41 mmol of diethylaluminum chloride (DEAC) with respect to the monomer, and 1,3-dichloro-2-propanol. (DCPr)
Was added so as to give a concentration of 41 mmol (Original reaction solution A). In the other container, tri (decyl) ammonium molybdate was added to the monomer so as to have a concentration of 10 mmol, and a phenolic antioxidant (manufactured by Ethanol Corporation, trade name: Ethanox 7) was added.
02) 4 parts were added (raw reaction B solution). A and B reaction stock solutions 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 top of a cavity maintained at 70 ° C. and having a thickness of 4 mm.
A flat plate of mm square was formed.

Glass transition temperature (Tg) of the obtained molded plate
Was measured with a differential scanning calorimeter (DSC) to find that
2 ° C. Further, the residual ratio of the weight of the polymer when heated from room temperature to 400 ° C. by a thermobalance was determined as the conversion, and was 98%. Flexural strength and flexural modulus (both measured at 23 ° C.) are each 7.2 kg / mm.
² and 190 kg / mm ² . The impact strength (Izod impact value, notched, measured at 23 ° C) is 40 kg
cm / cm ² . Almost no odor of the molded plate was observed. Next, the flat plate is pulverized to a size of about 2 mm with a sheet pelletizer (manufactured by Horai Iron Works), then pulverized to 500 μm or less with a pulverizer (manufactured by Tokyo Atomizer), and furthermore, a nitrogen atmosphere using a jet mill (manufactured by Fuji Sangyo). It was pulverized below to a size of 100 microns or less to obtain a resin powder.

[0031] Reference to Solution B 100 parts prepared in Example 1 Reference Example 1 Example 1
Were added at room temperature and mixed. Within 1 hour after mixing, the mixed solution and the solution A prepared in Reference Example A were mixed at a ratio of 1: 1 using a gear pump and a power mixer, and then injected into a mold maintained at 90 ° C. 4m
A 200 mm square flat plate was molded. The injection time was 15 seconds. About 40 seconds after the completion of the injection into the mold, smoke was observed, and 5 minutes later, the molded plate was removed from the mold.

The Tg of the obtained molded plate was 144 ° C. The conversion was 93%. The flexural strength and flexural modulus are 6.5 kg / mm ² and 180 kg / mm, respectively.
^{Was 2} . Impact strength (Izod impact value, with notch)
Was 34 kg · cm / cm ² . Although a slight odor was observed in the molded product, the odor was reduced to an almost inaudible level when heated at 100 ° C. for 1 hour.

Example 2 To 100 parts of the resin powder obtained in Reference Example 1, 25 parts of paraffin oil (SUNPAR110, manufactured by Nippon San Petroleum) was added, mixed in a vessel, heated to 50 ° C., and then degassed under reduced pressure. Then, the pressure was returned to normal pressure with nitrogen to obtain a paraffin oil-treated resin powder. Except for using this resin powder, bulk polymerization of a norbornene-based monomer was performed in the same manner as in Example 1 to obtain a molded product.

The Tg of the obtained molded plate was 136 ° C. No conversion was determined. The flexural strength and flexural modulus were 6.4 kg / mm ² and 180 kg / mm ² , respectively. Impact strength (Izod impact value, with notch) is 36kg
Cm / cm ² . Although a slight odor was observed in the molded product, the odor was reduced to an almost inaudible level when heated at 100 ° C. for 1 hour.

[0035]

According to the method of the present invention, a discarded norbornene-based resin molded product is reused as a molding material according to the present invention, whereby a molded product having good physical properties can be produced industrially. As shown in the above example,
The molded product obtained by the production method of the present invention has almost the same physical properties as a molded product obtained from a norbornene-based monomer without blending a pulverized norbornene-based resin molded product, and has a low odor. . Furthermore, in the production method of the present invention, the crushed norbornene-based resin molded product is mixed with the norbornene-based monomer and reused. Since it can be mixed with the molding material and reused, it is easy to obtain a material balance. Further, the resin molded product obtained by the production method of the present invention can be pulverized at the time of disposal, blended with the norbornene-based monomer again, and used as a raw material for molding.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-138222 (JP, A) JP-A-1-81817 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B29C 45/00-45/84 C08G 61/08

Claims (4)

(57) [Claims] 1. A norbornene-based resin molding, wherein a norbornene-based monomer is bulk-polymerized in a mold using a metathesis catalyst in the presence of a powder obtained by pulverizing a thermoset norbornene-based resin molded product. The method of manufacturing the product. 2. The method according to claim 1, wherein a reaction stock solution obtained by blending the powder and the metathesis catalyst with a monomer is subjected to polymerization. 3. The production method according to claim 2, wherein the polymerization is carried out before the viscosity of the undiluted reaction solution reaches twice the viscosity at the time of preparing the undiluted reaction solution. 4. The process according to claim 1, wherein the powder is treated with a high-boiling inert oil and then subjected to polymerization.