JPH03106961A - Production of polymer blend molding and combination of reactive solution - Google Patents

Abstract

PURPOSE:To produce a polymer blend molding excellent in the hardness, light resistance, flame retardance, etc., by dissolving a specific polystyrene resin in a metathesis-polymerizable monomer mainly comprising dicyclopentadiene and conducting the polymn. and molding of the resulting soln. simultaneously. CONSTITUTION:A process for producing a molding by simultaneously conducting the polymn. and molding of a metathesis-polymerizable monomer (e.g. ethylidene- norbornene) contg. at least 50wt.% dicyclopentadiene in the presence of a metathesis polymn. catalyst (e.g. a catalyst obtd. by treating tungsten hexachloride with nonylphenol and acetylacetone), wherein a low-mol.-wt. polystyrene resin (e.g. polystyrene) having a number-average mol.wt. of 400-80000 in an amt. of 3-50wt.% based on the molding is dissolved in the monomer.

Description

[Detailed Description of the Invention] a. INDUSTRIAL APPLICATION FIELD The present invention relates to an improved method for producing a crosslinked polymer molded product obtained by simultaneously polymerizing and molding a metasense polymerizable monomer mainly composed of dicyclopentadiene in the presence of a metasense polymerization catalyst. It is. More specifically, the present invention relates to a manufacturing method for obtaining a molded blend polymer with a metasense polymer by dissolving low molecular weight polystyrene in the monomer during the above polymerization.

b. BACKGROUND OF THE INVENTION It is known that strained cyclic olefins undergo ring-opening polymerization using metasense polymerization catalyst systems. Utilizing this, a monomer such as dicyclopentadiene that is inexpensively obtained and has two metasense polymerizable cyclic olefin groups is poured into a mold in a liquid state, and bulk polymerization is performed therein.
A method of performing polymerization and molding in one step has been proposed (see, for example, Japanese Patent Application Laid-open No. 129013/1983).

According to this method, a large-sized molded product can be obtained using an inexpensive mold, so it has the possibility of being used in a wide range of applications.

However, such molded products have different requirements depending on their use, and various characteristics are required as necessary.

As a method for modifying such properties, a method using a polymer blend is generally used. However, the poly(
In the case of cross-linked polymers such as dicyclopentadiene, it is impossible to blend them in the polymer form afterward, and it is necessary to dissolve them in monomers in advance, and the monomers cannot be polymerized. In this case, if the polymer does not have a certain level of compatibility or affinity with the resulting polymer, phase separation of the two polymers will occur during polymerization, and only a non-uniform, defect-free blend will be obtained. There won't be any.

That is, in order to use it as a blend for the above purpose, it must be soluble in monomers mainly consisting of dicyclopentadiene,
In addition, it must have sufficient affinity with the metasense polymer to prevent significant phase separation during polymerization.

However, it is preferable to mold such a reactive solution by rapidly mixing it and pouring it into a mold, such as a reaction indexing or molding method, but in such a case, the viscosity of the reactive solution is below a certain level, generally , it is preferable that the liquid temperature at the time of injection is 1000 cps or less.

This means that when a high molecular weight polymer is dissolved, the solution viscosity will reach this viscosity after only a few percent of the polymer has been dissolved. There will generally be a shortage of quantity. Therefore, the material used in such a blend must have a relatively low molecular weight that can be easily obtained and still exhibit the properties of the polymer.

Furthermore, even if such a polymer is obtained with a low molecular weight, it must be able to be used without inhibiting the activity of the metasense polymerization catalyst system even if it coexists in solution.

As a result of intensive studies to find a polymer from which a blended resin can be obtained that satisfies these requirements and exhibits high practicality, the present inventor found that a medium to low molecular weight polystyrene resin with a specific molecular weight satisfies these characteristics. This is what led to the present invention.

C6 Structure of the Invention The present invention comprises: (1) Production of a polymer molded product by simultaneously polymerizing and molding a metasense polymerizable monomer in which at least 50% by weight of the monomer is dicyclopentadiene in the coexistence of a metasense polymerization catalyst. A method for producing a blend polymer molded article, characterized in that a low molecular weight polystyrene resin having a number average molecular weight of 400 to 80,000 is dissolved and added to a monomer at a ratio of 3 to 50% by weight to the molded article.

(2) A reactive solution of a metasense polymer monomer containing a catalyst component of a metasense polymerization catalyst system (solution A), and a reactive solution of a metasense polymerizable monomer containing a certain amount of an activator of a metasense polymerization catalyst system (solution B) at least 50% by weight of the total amount of the metasense polymerizable monomer is dicyclopentadiene, and a low molecular weight polystyrene resin with a number average molecular weight of 1 400 to 80,000 is added in an amount of 3 to 50% by weight based on the entire solution. A combination of reactive solutions characterized in that they are dissolved and added to at least one of the solutions in proportion.

In other words, polystyrene resins are highly soluble in cyclic olefin monomers mainly composed of dicyclobentadiene, and have good compatibility not only with monomers but also with crosslinked polymers obtained by metasense polymerization of monomers mainly composed of dicyclopentadiene. Because of its solubility and its polymerization properties, polystyrene resins undergo radical polymerization, anionic polymerization, and cationic polymerization. All types of polymerization occur easily, and by using each properly, it is possible to commercially obtain products with a number average molecular weight ranging from a low molecular weight of several hundred to a medium molecular weight of several thousand to tens of thousands and a high molecular weight of over 100,000. Furthermore, in addition to simple polystyrene homopolymer, there are also polystyrene copolymerized with a small amount of other monomers, polyvinyltoluene, which can be called a styrene derivative, poly-alpha-methylstyrene, and halogenated polystyrene, such as bromine. It can meet all the requirements as a blending resin for poly(dicyclopentadiene) crosslinked polymers, such as the availability of low to medium molecular weight products such as chlorinated polystyrene and chlorinated polystyrene. This was discovered as a result of consideration.

Such polystyrene resin has a main chain composed of a saturated hydrocarbon and a stable phenyl group in the side chain, and a poly(dicyclopentadiene) cross-linked polymer whose main chain is composed of an unsaturated hydrocarbon and a cyclic olefin. It has been found that it is possible to eliminate the drawbacks of the latter without impairing its characteristics.

For example, although it is tough, it contains a large amount of unsaturated hydrocarbons, so it is possible to improve the light resistance and hardness of the surface, and if brominated polystyrene is used, it is possible to improve flame retardancy. Furthermore, when a large amount of low molecular weight polystyrene is blended, it becomes a crosslinked polymer, and it becomes possible to impart fusibility to a resin that does not have fusibility.

In addition to styrene, the polystyrene resin used in the present invention includes polymers of styrene monomers that are lower alkyl-substituted and/or halogen-substituted styrene and have similar polymerizability.

Such polystyrenes include polystyrene, poly-
Examples include p-, -1- or 101-vinyltoluene, polyvinylxylene, poly-α-methylstyrene, brominated polystyrene, and chlorinated polystyrene.

Furthermore, polystyrene resins in the present invention also include those copolymerized with other monomers, generally not exceeding 30 mol%, more preferably within 10 mol%, with the above styrene monomers. However, such copolymerized monomers are
It is required that it has no functional groups that would inhibit the metasense polymerization catalyst. Examples of such copolymerizable monomers include methyl methacrylate, methyl acrylate, butadiene, isobrene, and the like.

The polystyrene resin used in the present invention has a number average molecular weight of 400 to 80,000.

If the number average molecular weight is less than 400, it tends to become liquid at room temperature, and if it is more than 80,000, as mentioned above, the viscosity of the monomer solution becomes too high even with a small amount dissolved, which is not preferable. More preferably 900-60
,000 is preferred.

Generally, those having a number average molecular weight of 900 to 5,000 are used for such purposes because they can be added in a sufficient amount to exhibit functions such as fusion properties and flame retardancy. On the other hand, a polystyrene resin having a number average molecular weight of s,000 to 80,000, especially 20,000 to 60,000, imparts to the metasense polymer the properties inherent to polystyrene, such as planar hardness and light resistance. used for

The amount to be added is in the range of 3 to 50% by weight, and particularly preferably in the range of 10 to 35% by weight.

The present invention uses dicyclopentadiene as the main monomer. When used as a raw monomer, it is used in an amount of at least 50% by weight or more, more preferably 75% by weight or more, still more preferably 90% by weight or more of the total monomers.

In the combination of reactive solutions, at least 50% by weight of the total amount of metasense polymerizable monomers in solution A and solution B
is preferably dicyclopentadiene.

As the metasense polymerizable monomer used with dicyclopentadiene, other cyclic olefins having a norbornene structure or equivalent metasense polymerizability 1
Monomers having ~3 monomers can be mentioned.

Preferred specific examples include oligocyclopentadiene such as tricyclopentadiene, ethylidenenorbornene, norbornene, 5-methylnorbornene. norbornadiene, 6-ethylidene-1.4.5.8-dimethano-1.
4,4a,5,6,7,8,8a-octahyde-naphthalene, 1,4,5.8-dimethano-1.4,4a,5,
8,8a-hexahide naphthalene, 1,4,5.8-
Dimethano-1.4,4a,5,6,7,8.8a-octahyde naphthalene, 6-methyl-1.4,5.8-
Dimethano-1,4,4a,5,6,7,8.8a-octahyde naphthalene and the like can be mentioned.

Furthermore, metasense polymerizable cycloolefin monomers containing different elements such as oxygen and nitrogen can also be used, if necessary. Such polar monomers are often used in copolymerization with dicyclopentadiene or the like, for example, in an amount of about 1 to 20% by weight.

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

Specific examples of such copolymerizable monomers include 5-methoxycarbonylinolenolebornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, 5-
Phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano1.4,5.8-dimethano-1.4
．． Examples include 4a, 5, 6, 7, 8.8a-octahyde naphthalene, N-butylnadic acid imide, and the like.

As mentioned above, the metasense polymerizable monomer is required to contain as few impurities as possible that would inactivate the metasense polymerization catalyst.

As the main catalyst component in the metasense polymerization catalyst system used in the present invention, salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used, and compounds of tungsten and molybdenum are preferred, and tungsten compounds are particularly preferred.

Such tungsten compounds are preferably tungsten halide, tungsten oxyhalide, tungstate, and more specifically, tungsten hexachloride. Tungsten oxychloride and the like are preferred. Such tungsten salt compounds are known to immediately start cationic polymerization when added directly to monomers, which is not preferred. Therefore, tungsten salt compounds can be used in inert solvents such as benzene and 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 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. An example of such an additive is acetylacetone. Acetoacetic acid alkyl esters. Examples include tetrahydrofuran and penzonitrile. In addition, soluble catalysts such as ammonium tungstate salts can also be used.

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 metasense polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals of Groups 1 to 2 of the periodic table, particularly tetraalkyl tin, alkylaluminum compounds, and alkylaluminium halide compounds. Specifically, diethylaluminum chloride. Ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide. Tetrabutyltin. Examples include tributyltin hydride. These organometallic compounds as activator components,
The other solution (corresponding to solution B) is formed by dissolving it in the raw material monomer.

The polystyrene resin used in the present invention is generally used in the above-mentioned reactive solution A. It is used after being added and dissolved in either or both of B.

Above A. When both liquids B are used in the reaction extrusion molding method, the mixing efficiency is better when both liquids have the same viscosity, so it is preferable that the polystyrene resin is also dissolved in both liquids A and B to the same extent. However, depending on the type of polystyrene resin with a low degree of polymerization, there may be some that interact with either the main catalyst component or the activator component of the metasense polymerization catalyst and gradually reduce its activity. It is preferable to use it by dissolving it only in the liquid containing the catalyst system component with the smaller interaction. Such interactions can be easily determined by dissolving the resin in a solution containing one of the catalyst components and cross-checking the solution at appropriate times during long-term storage with a standard solution to which it is not added.

In the present invention, a crosslinked polymer molded product can basically be obtained by mixing the solutions A and B, but if the above composition remains as it is, the polymerization reaction will start very quickly. Hardening may occur before it has sufficiently flowed into the mold, which is often a problem, and as mentioned above, it is preferable to use an activity modifier for this purpose.

As such regulators, Lewis bases are generally used, especially ethers, esters. Nitriles etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. Although such a modifier can be added to both solutions, generally, it may be more effective to add it to the side of the solution containing the activator component of the organometallic compound. If a monomer having a Lewis space group is used as described above, it can also serve as a regulator.

The amount of the metasense 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 raw material monomer is about 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
and when using an activator or alkyl aluminum, the ratio is about 100 to 1 to about 2 on a molar basis.
000:1, preferably around 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.

The blend crosslinked polymer molded product produced by the production method of the present invention is
In order to improve or maintain its characteristics in practical use,
In addition to the polystyrene resin described above, various additives may be further blended. Such additives include fillers,
Pigments, antioxidants, light stabilizers, flame retardants, and polymer modifiers other than the above polystyrene resins. There are plasticizers, etc. As with the above-mentioned polystyrene resin in the present invention, it is impossible to add such additives after the crosslinked polymer has been formed into a certain shape. It is necessary to keep it.

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 activator in the liquid to a certain extent for practical purposes. In addition, it must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it can be mixed with the monomer to prepare a third liquid and mixed and used immediately before assembly. . In addition, in the case of solid fillers, if the components are mixed and have a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization, it is necessary to fill the voids in the mold. It is also possible to pre-fill.

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

In addition, it is preferable to add an antioxidant to the blended cross-linked polymerized and suspended product produced by the production method of the present invention, and therefore it is desirable to add a phenolic or amine-based antioxidant to the solution in advance. . Specific examples of these antioxidants include 2.61°C-Petyl-P-cresol;
N,N'-diphenyl-P-7enylene diamine, tetrakis[methylene(3,5-di-t-butyl-4-hydroxycinnamate)]methane, and the like.

Further, in the polymer molded product produced by the production method of the present invention, other polymers other than the polystyrene resin can be added, especially in the form of a reactive solution.

Such a polymer modifier is preferably one that is effective when added in a few percent due to its nature, and can improve the impact resistance, which is a major problem with the blend polymer of the present invention, and improve the properties of polystyrene resins. A. It is used for purposes such as adjusting the viscosity of the opposite side when dissolved in a solution of only one of B. From this point of view, it is preferable to add a soluble elastomer.

Such soluble elastomers preferably have a certain degree of affinity for both poly(dicyclopetane dienes) and polystyrene resins, and include styrene-butadiene-styrene triblock rubber, styrene-isobrene-styrene triblock rubber, and the like. Preferred are olefin-part hydrogenated rubber, styrene-butadiene rubber, ethylene brobylene rubber, ethylene brobylene diethane polymer, and the like.

Particularly, when the polystyrene resin is dissolved in the same solution as the polystyrene resin, phase separation tends to occur, so a material with a high styrene content is preferably used.

A plasticizer can also be added to the blend molded product of the present invention. As the plasticizer, from the viewpoint of compatibility with the resin, alkyl-substituted aromatic compounds such as dodecylbenzene, triethylpifenyl, or halogenated hydrocarbons such as chlorinated paraffin, brominated dodecylbenzene, etc. are used. I can do things.

Furthermore, if a large amount of residual monomer remains in the molded product of the present invention, a unique depth may appear. As such a residual monomer reducing agent, α. α. Examples include α-trichlorotoluene, dichlorodiphenylmethane, trichloroacetic acid ester, phthalic acid chloride, benzoic anhydride, phosphorus oxychloride, benzenesulfonic acid chloride, and the like. Furthermore, color pigments, light stabilizers, and, if necessary, flame retardants other than halogenated polystyrene. A blowing agent etc. can also be added and used.

The present invention is carried out by simultaneously carrying out polymerization and molding using a combination of the reactive solutions as described above.

As mentioned above, such molding methods include mixing the catalyst and raw material monomer with a simple mixer such as a static mixer, resin injection method in which a pre-mixed premix is flowed into a mold, and catalyst molding method. It is possible to adopt the RIM method in which the system is divided into two parts, solution A and solution B, which are collided and mixed in a head section and poured into a mold as they are. In particular, the RIM method is commonly used.

In either case, the injection pressure into the mold can be relatively low, making it possible to use inexpensive molds. Further, when the polymerization reaction inside the mold starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time.

Unlike polyurethane-RIM, it is easy to release from the mold and often does not require a special mold release agent.

d. Effects of the Invention The blended molded product thus obtained has additional characteristics such as hardness, light resistance, flame retardance, and fusion properties due to the blended polystyrene resin, and can be used as a molded product for housings of various devices. It can be used for a wide range of purposes, including

e. EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. Note that the examples are for illustrative purposes only, and are not limited thereto.

Example 1, Comparative Example 1 Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified cydiclopentadiene having a freezing point of 33.4°C.

Purity measurement using a gas chromatograph showed a purity of 99% or more.

Purity measurement using gas chromatography using commercially available high-purity ethylidene norbornene (ENB) as a monomer showed 99% or more.

[Preparation of main catalyst concentrate] High purity tungsten hexachloride 19.80 9 (0.
05 mol) was added to 90 liters of dry toluene under a nitrogen stream, 0.925 g of t-butanol dissolved in 5 liters of toluene was added, stirred for 1 hour, and then nonylphenol 11.05 9 (0.05 mol) and toluene 5d
Add the solution and stir for 1 hour under a nitrogen purge.

10 g of acetylacetone was added to the mixture and stirring was continued overnight under a nitrogen purge while driving off by-product hydrogen chloride gas, then some of the toluene distilled out was supplemented to 0.5 M
A tungsten-containing catalyst concentrate was prepared.

[Preparation of activator concentrate] G-n-octyl aluminum iodide 5.70
g. Tri-10-octyl aluminum 31.17!
? , diglyme 13.42 9 were mixed under a nitrogen stream,
Then, DCP was added to dilute the entire solution to 100% to obtain a 1.0M aluminum-containing activator concentrate.

[Preparation of reactive solution A] Dicyclobetane diene, ethylidene norbornene. Manufactured by Dainippon Ink■. Elastyrene #200 (number average molecular weight 40,000±s,000) in a weight ratio of 78:2:2
E tha for the solution 1 000 9 mixed and dissolved at 0
nox702 209, main catalyst solution 13.0cc
were mixed under an inert atmosphere to obtain reactive solution A.

[Preparation of Reactive Solution B] To 1000 g of the solution mixed in the same ratio as above, 33. 3 cc were mixed under an inert atmosphere to form Reactive Solution B.

Using these solutions A and B, the mold temperature was set at 100°C/80°C for the upper and lower sides using a micro RIM machine, and the temperature was set at 3aw+
A thick molded plate was molded.

For comparison, when polystyrene is not used, that is, dicyclopentadiene, ethylidene norbornene 9
1:3 mixed solution, 16.2cc of the main catalyst solution, 23.2cc of activator concentrate. A 3jIIl thick precept plate was molded in exactly the same manner except that 7cc was used.

The polystyrene-containing board is transparent, has a hard surface, and seems to have increased rigidity, and its appearance is improved compared to the comparative board. When measuring the bending modulus, it is 23
000K9/rd, 17000N#/ on the comparison board
It was confirmed that it was significantly improved compared to cIi. 1
When the heat distortion temperature and notched Izod under a 6.5K9/ai load were measured, the plate of the example was 87'C.4.
3K9aa/cm, and the comparative example was 89℃, 4,8
89α/α, and it can be seen that the basic performance is almost unchanged, but the above characteristics have been improved, making it a molded product suitable for use in housings. Example 2 [Reactive solution B manufactured by lil] Dicyclopetane diene, ethylindenorbornene. Prototype brominated polystyrene (bromine content 69.2 wt%, polystyrene equivalent number average molecular weight 550, weight average molecular weight/number average molecule 12.2) in a weight ratio of 48:1.5:
54 cc of the same activator concentrate as used in Example 1 was mixed in an inert atmosphere with 1000 9 of the solution mixed and dissolved in 50.5 to obtain a reactive solution B.

[Preparation of reactive solution A] Dicyclopentadiene, ethylindenorbornene, Mitsui Petrochemical EPT-4070 ethylene brobylene polymer rubber in a weight ratio of 93/3/4
20 g of EthanOX702 manufactured by Ethyl Co., Ltd., Example 1 to 1000 9 of the solution mixed and dissolved at the ratio of
1 ecc of the same activator concentrate used in Example 1 was mixed under an inert atmosphere to form Reactive Solution A.

This solution A. A 3M thick mold plate was molded using B and an ultra-small RIMtl under the same conditions as in Example 1. The resulting molded plate had a strong brown color due to the brominated polystyrene, but the surface and overall hardness were improved as before.

The bending modulus was 20, OOOK9/ai, and it can be confirmed that it is greatly improved compared to the comparative example in which no polystyrene is added. The heat distortion temperature and notched Izod under a 16.5K9/ci load were measured at 90°C.
, 1289ax/a.

Such molded plates comply with JIS K-6911 and HiLJL94.
When a flame retardant test was conducted using the V method, the former was 2a.
The fire extinguished at m, and the grade became nonflammable, and the latter passed the ■1 grade, showing good flame retardancy.

This shows that a resin molded product with improved flame retardance and suitable for housings of electronic devices and the like can be obtained without compromising basic performance.

Claims (2)

[Claims] (1) A method for producing a polymer molded product by simultaneously polymerizing and molding a metasense polymerizable monomer in which at least 50% by weight of the monomer is dicyclopentadiene in the coexistence of a metasense polymerization catalyst.
A method for producing a blend polymer molded article, characterized in that a low molecular weight polystyrene resin having a molecular weight of 0 to 80,000 is added to the molded article by dissolving it in a monomer at a ratio of 3 to 50% by weight. (2) From a reactive solution of metasense polymer monomers containing a catalyst component of a metasense polymerization catalyst system (solution A) and a reactive solution of metasense polymerizable monomers containing an activator component of a metasense polymerization catalyst system (solution B) at least 50% of the total amount of said metasense polymerizable monomers
A low molecular weight polystyrene resin whose weight% is dicyclopentadiene and whose number average molecular weight is 400 to 80,000 is dissolved and added to at least one side of the solution at a ratio of 3 to 50% by weight based on the entire solution. A combination of reactive solutions.