JPH05262856A - 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 norbornene monomer is bulk polymerized in a mold using a metathesis catalyst in the presence of a powder obtd. by pulverizing a waste norbornene molding. Flashes, gates, rejected parts, etc., formed in the molding step are thus mixed into the monomer 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 that the waste generated in the molding process be reused in the same process from the viewpoint of mass balance and economical rationality such as labor for transfer and storage.

No attempts have been made so far to crush a norbornene-based resin molded product into powder, add this to a norbornene-based monomer as a filler, and reuse it for molding a norbornene-based resin. This is because the surface of the norbornene-based resin molded product is easily oxidized, and thus it is considered that the powder obtained by crushing the molded product is more likely to be oxidized, and therefore, the powder is considerably oxidized during storage. This is because it is predicted that if this is advanced and compounded in a polymerization raw material, polymerization inhibition will occur.

[0007]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventors have made a study on reusing a norbornene-based resin molded product as a resin molding material. As a result, the powder obtained by crushing a norbornene-based resin molded product is norbornene. Unexpectedly, the blended liquid obtained by blending with the system monomer does not deteriorate 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 the bulk polymerization with the metathesis catalyst. I found it. 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.

[0009]

DISCLOSURE OF THE INVENTION The present invention is directed to bulk polymerization of norbornene-based monomers in a mold using a metathesis catalyst in the presence of powder obtained by crushing a thermosetting norbornene-based resin molded product. A method for producing a characteristic norbornene-based resin molded product 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 crushed and reused in the form of powder. The powder is obtained by, for example, shredding with a pelletizer, a grinder, a cutter or the like into chips, and then pulverizing with a ball mill, a jet mill, a pulsarizer or the like. Micronization can be done in air,
Considering the risk of dust explosion, it is preferable to carry out in nitrogen or other inert gas.

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. However, if the particle size is excessively small, there is a problem that the particle rapidly swells when mixed with the monomer.

The catalyst remaining in the thermosetting norbornene-based resin molded product to be reused is a metathesis catalyst. 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 the norbornene-based monomer in the mold by using the powder of the norbornene-based resin molded product, a reaction stock solution obtained by mixing the powder and the metathesis cocatalyst with the norbornene-based monomer is used. It is preferable that a substantially non-swelled state (Liquid B) and a reaction stock solution (Liquid A) containing a norbornene-based monomer and a metathesis cocatalyst are mixed, and this mixed liquid is subjected to bulk polymerization in a mold.

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

The reason why the pulverized product in the liquid B is mixed with the liquid A while it is in a substantially non-swelling state is as follows. When the resin pulverized product is swollen in the liquid B and the monomer is allowed to penetrate into the spaces between the pulverized product particles and then mixed with the liquid A and reacted at a high reaction rate, the monomer in the space between the pulverized products is converted into the liquid A. Since the co-catalyst of No. 1 is hardened on the peripheral surface of the pulverized product particles before sufficiently diffusing, unreacted monomer remains in the interstices between the particles, resulting in deterioration of the physical properties of the molded product and odor from the molded product. Occur.

Since the active metathesis catalyst remains in the crushed product of the norbornene resin molded product, this crushed 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 blended amount of the pulverized resin molded product in the liquid B is preferably 1 to 60% by weight, and 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 will increase, making it difficult to handle.

The crushed product of the 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 point inert oil, the gaps between the pulverized particles are blocked with the inert oil, and the permeation of the monomer is blocked. Therefore, the amount of residual unreacted monomer in the obtained molded product can be significantly reduced, and odor is completely eliminated. The high-boiling inert oil is preferably a hydrocarbon oil having a boiling point of 180 ° C. or higher and a halogenated hydrocarbon oil. Specific examples thereof include paraffin oil, naphthene oil, aroma oil,
Examples include chlorinated paraffin.

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 liquids A and B, the mixed liquid 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 perform 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.

The catalyst used for preparing the liquid B is a metathesis catalyst known as a catalyst for ring-opening polymerization of norbornene type monomers (for example, Japanese Patent Application No. 58-127728,
No. 58-129013) are used and there is no particular limitation. Examples of metathesis catalysts include:
Examples include halides such as tungsten, molybdenum, and tantalum, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyacid salts. Among these, tungsten and molybdenum organic materials that are stable to water and oxygen are particularly preferable. 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 tricapryl ammonium molybdate and tungstate, tri- (tridecyl) ammonium molybdate and tungstate, and trioctyl ammonium molybdenum. Examples thereof include acid salts and tungsten chloride.

The amount of the metathesis catalyst used is as follows.
It is usually used in an amount of 0.01 to 50 mmol, preferably 0.05 to 5 mmol, based on 1 mol of the norbornene-based monomer in the liquid. The cocatalyst is usually 0.1 to 200 (molar ratio), preferably 1 to 1 with respect to the catalyst component.
It is used in the range of 0 (molar ratio).

Examples of the cocatalyst used for preparing the liquid A include organometallic compounds having a function of reducing the metathesis catalyst conventionally used in 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.

In the liquid A, an activator can be used 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 the metathesis catalyst which may be optionally added in the preparation of the liquid B, the organic ammonium salts of tungsten and molybdenum and oxyhalogen compounds such as phenoxy halogen compounds are preferably used as described above. 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.

A crosslinking agent such as sulfur or peroxide and a vulcanization accelerator thereof can be added to the liquid B, if desired. When these are added, the heat resistance of the molded product is improved, and the generation of odor is more completely prevented. The addition amount is preferably equal to or less than that of the crushed 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 becomes 150 to 250 ° C. during molding, but in the case of a thick-walled molded product, since the maintenance time at this temperature is long, crosslinking is facilitated, heat resistance is improved, and odor generation is suppressed. To be done.
After the molding in the mold is completed, it can be taken out from the mold and subjected to an aging reaction in a heating furnace or the like.

Various additives can be added to either or both of the liquid A and the liquid B, depending on the desired characteristics of the obtained 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.

[0029]

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%. Flexural strength and flexural modulus (each measured at 23 ° C) are 7.2 kg / mm
² and 190 kg / mm ² . The impact strength (Izod impact value, notched, measured at 23 ° C) is 40 kg.
It was cm / cm ² . Almost no odor of the molded plate was observed. Then, the flat plate was crushed to a size of about 2 mm with a sheet pelletizer (manufactured by Tomo Tekko Co., Ltd.), then crushed to 500 microns or less by a palberizer (manufactured by Tokyo Atomizer), and further, a nitrogen atmosphere using a jet mill (manufactured by Fuji Sangyo). The resin powder was obtained by pulverizing the powder to a size of 100 microns or less.

[0031] Reference to Solution B 100 parts prepared in Example 1 Reference Example 1 Example 1
20 parts of the powder obtained in 1. was added and mixed at room temperature. Within 1 hour from the mixing, this 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 poured into a mold maintained at 90 ° C. 4m
A flat plate of m and 200 mm square was formed. The injection time was 15 seconds. Smoke was observed about 40 seconds 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 144 ° C. The conversion rate was 93%. 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 . A slight odor was observed in the molded product, but when it was heated at 100 ° C. for 1 hour, it decreased to an almost unnoticeable level.

Example 2 To 100 parts of the resin powder obtained in Reference Example 1 was added 25 parts of paraffin oil (SUNPAR110, manufactured by Nippon Sun Oil Co., Ltd.), mixed in a container and heated to 50 ° C., and then deaerated under reduced pressure. Then, the pressure was returned to normal pressure with nitrogen to obtain a paraffin oil-treated resin powder. Bulk polymerization of the norbornene-based monomer was carried out in the same manner as in Example 1 except that this resin powder was used 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, notched) 36kg
・ It was cm / cm ² . A slight odor was observed in the molded product, but when it was heated at 100 ° C. for 1 hour, it decreased to an almost unnoticeable level.

[0035]

Industrial Applicability A molded product having good physical properties can be industrially manufactured by reusing the crushed product of the discarded norbornene resin molded product as a molding raw material according to the method of the present invention. As shown in the examples above,
The molded product obtained by the production method of the present invention has physical properties comparable to those of the molded product obtained from the norbornene-based monomer without blending the crushed product of the norbornene-based resin molded product, and has less 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 (4)

[Claims] 1. A norbornene-based resin molded article characterized by bulk polymerizing a norbornene-based monomer in a mold using a metathesis catalyst in the presence of a powder obtained by crushing a thermosetting norbornene-based resin molded article. Manufacturing method. 2. The method according to claim 1, wherein a reaction stock solution obtained by mixing the powder and a metathesis catalyst in a monomer is subjected to polymerization. 3. The method according to claim 2, wherein the polymerization is carried out before the viscosity of the reaction stock solution reaches twice the viscosity at the time of preparing the reaction stock solution. 4. The production method according to claim 1, wherein the powder is treated with a high boiling point inert oil and then subjected to polymerization.