JPH02269733A - Production of plasticized polymer molding and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To obtain a plasticized polymer molding excellent in impact resistance by mixing a cycloolefin monomer containing a catalyst component of a metathesis polymerization catalyst system with a monomer containing both an activator component of the catalyst system and a halogenated paraffin and polymerizing and molding the obtained mixture. CONSTITUTION:A reactive solution of a metathesis-polymerizable cycloolefin monomer (e.g. dicyclopentadiene) containing a catalyst component (e.g. tungsten hexachloride) of a metathesis polymerization catalyst is mixed with another reactive solution of a metathesis-polymerizable cycloolefin monomer containing both an activator component (e.g. diethylaluminum chloride) of the metathesis catalyst system and a halogenated paraffin as a plasticizer (e.g. chlorinated paraffin). The obtained mixture is simultaneously subjected to molding and polymerization to obtain a plasticized polymer molding.

Description

Detailed Description of the Invention a. Industrial Application Field The present invention provides an improved method for plasticizing a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst. It is related to. More particularly, the present invention relates to improved methods for using halogenated paraffins as plasticizers in metathesized polymer moldings.

b. Prior Art It is known that strained cyclic olefins undergo ring-opening polymerization using a metathesis polymerization catalyst system. Utilizing this, a monomer such as dicyclopentadiene, which is inexpensively obtained and has two metathesis-polymerizable cyclic olefin groups, is poured into a mold in a liquid state, and bulk polymerization is performed therein. A method of performing molding in one step has been proposed (see, for example, Japanese Patent 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, depending on the application, such molded products are often required to be plasticized in order to improve their impact resistance.

Such plasticizing methods include, for example, US Pat. No. 4,485.
No. 208 has a trussility parameter of 7.8 to 10.
．． The use of ester plasticizers of No. 2 has been proposed. On the other hand, metathesis polymers from cyclic olefins, such as polydicyclopentadiene, have a strubility parameter of about 9.3, according to measurements by the present inventor.
In this respect, the above ester plasticizers seem to have a strong affinity, but while poly(dicyclopentadiene) has a structure that does not have hydrogen bonds, esters have a weak but strong affinity for hydrogen bonds. Therefore, there is a concern that even if the trussibility parameters are similar, the affinity may not be great. In fact, when measured, the swelling ratio of the poly(dicyclopentadiene) with an ester solvent having a sturdiness parameter of 9.0 to 9.5 is very small.

On the other hand, it has been found that halogenated hydrocarbons and aromatic hydrocarbons such as chloroform and toluene, which have a trubility parameter of 9.0 to 9.5, exhibit a large swelling ratio. Therefore, the present inventor came up with the idea of using halogenated paraffins having a halogenated hydrocarbon as a basic structure as a plasticizer for such polymers.

Halogenated paraffins, especially chlorinated paraffins,
It is known to be available at low cost as a plasticizer for vinyl chloride and to have no concerns about toxicity.

Furthermore, since the above-mentioned cycloolefin metathesis polymers are generally composed of hydrocarbons, they are often easily flammable. Therefore, it is preferable to suppress flammability as much as possible, but halogenated paraffins contain a considerable amount of halogen. Therefore, it should be effective in reducing flammability, and is preferable in that respect as well.

However, when attempting to carry out metathesis polymerization in the presence of chlorinated paraffin, which is a typical industrially available halogenated paraffin, it has been found that it has a polymerization inhibiting effect. On the other hand, when 1,3-dichlorobencune, which can be called a model compound of halogenated paraffins, coexists, it is found that it does not inhibit metathesis polymerization at all, and halogenated hydrocarbons themselves generally inhibit metathesis polymerization. That will never happen.

As is well known, halogenated paraffins are halogenated by blowing halogen into paraffins, but since they cannot be purified as they are, in the process of halogenation, the hydrogen atoms and halogen atoms of simple hydrocarbons are It is speculated that another functional group is generated by a side reaction other than substitution, and this seems to inhibit metathesis polymerization. However, it is not well known what such inhibitory groups are, and therefore, no method has been found to suppress their inhibitory properties. Therefore, the inventor of the present invention has arrived at the present invention as a result of intensive research into what means are possible for using halogenated paraffins as a plasticizer (and flame retardant in some cases) for metathesis polymers. It is something.

The structure of the C9 invention is that the inhibiting group in the halogenated paraffin reacts relatively quickly with the active component of the metathesis polymerization catalyst,
They have discovered that if it is consumed or its reaction content is supplemented, it will remain stable and will no longer inhibit polymerization. On the other hand, it was discovered that when added to the main catalyst component solution, the inhibitory effect does not stop for a long period of time, making it difficult to put it into practical use.

The present invention includes the following inventions.

(1) A reactive solution (solution A) of a metathesis polymerizable cycloolefin monomer containing a catalyst component of a metathesis polymerization catalyst system and a reactive solution (solution A) of a metathesis polymerizable cycloolefin monomer containing an active agent component of a metathesis polymerization catalyst system. A method for producing a plasticized polymer molded product by mixing at least B) and molding at the same time, characterized in that a halogenated baraf, in is added to the solution B. .

(2) A reactive solution of a metathesis-polymerizable cycloolefin monomer containing the catalyst component of the metathesis polymerization catalyst system (solution A) and a reactive solution of the metathesis-polymerizable cycloolefin monomer containing the active component of the metathesis polymerization catalyst system (solution B). A combination of reactive solutions consisting of at least one of the following: 1.) A halogenated paraffin is added to the solution B.

The halogenated paraffin used in the present invention is
Generally, paraffin wax is directly halogenated with chlorine and/or bromine from liquid paraffin with an average carbon number of about 10 to 30, and the halogen content is 30 to 80% by weight.
They range from liquid to solid at room temperature, and are generally commercially available as chlorinated paraffin, chlorinated brominated paraffin, and brominated paraffin, and are used as plasticizers, rubber compounding agents for vinyl chloride resin, paint compounding agents, fibers and wood. Those used as fireproofing agents, polyurethane flame retardants, lubricating oil additives, etc. can be used as they are.

Especially when the average molecular weight is around 350 to 550, the chlorine content is 40
~70 wt% low molecular normal paraffin type, average molecular weight around 500-1100, and similarly chlorine content 40-70
Each chlorinated paraffin of wt% paraffin wax type, chlorinated or brominated paraffin containing about 20 to 35 wt% of both chlorine and bromine, brominated paraffin containing 30 to 50 wt% of only bromine, etc. are used. be able to.

For plasticization purposes only, chlorinated paraffins, even ones with a low chlorine content, are sufficient; however, when good flame retardancy is also desired, bromine-containing paraffins and It is preferable to use paraffins containing as much chlorine as possible.

On the other hand, the type and amount of by-product groups that can react with the activator have traditionally been left to chance, as there was no need for manufacturers to control them, and they vary depending on the product. And because it is not controlled, there can be lot-to-lot variation.

Therefore, when implementing and using the present invention, it is sufficient to select an appropriate one by testing by the method described in detail in the examples and carefully confirming the number of people involved.

Regarding the amount of chlorinated paraffin added, the degree of plasticization required will differ depending on the purpose of use of the molded product, and the degree of flame retardation will also differ, so it is sufficient to select the amount that matches the purpose. It turns out. - most preferably 3 to 35 wt%, more preferably 5 to 25 wt% of total monomers
A range of % is used.

Preferred specific examples of the metathesis-polymerizable cycloolefin monomer used in the present invention include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, norbornadiene, -Cyclohexenylnorbornene.

1,4.5.8-dimethano-1,4,4a, 5.6.
7.8.8.8a-Octahydronaphthalene, ■, 4-
Methanol 1.4.4a, 56,7,8,8.8a-octahydronaphthalene, 6-nitylidene-1.4.5.
8-dimethano-1,4,4a, 5.6.7.8.8a
-heptahydro-naphthalene, 6-methyl-1,4,5
, 8-dimethano-1,4,4a, 5.6.7.8.8
1 to a-1 Tahid naphthalene, 1,4,5,8-dimethanol-1,4゜4a, 5,8,8a-hexahydronaphthalene, ethylene bis(5-norbornene), etc.
Examples include one or a mixture of two or more cyclic olefins having ~3 norbornene structures, and dicyclopentadiene or a monomer mixture mainly composed of dicyclopentadiene is particularly preferably used.

Furthermore, metathesis-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 polar monomers also preferably have a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide, or the like.

Specific examples of such copolymerizable monomers include 5-methoxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, and 5-phenyloxymethylnorbornene.

5-cyanonorbornene, 6-diatu 1.4.5.8
-dimethano-1,4,4a, 5.6.7.8.8a-
Examples include octahydronaphthalene and N-butylnadic acid imide.

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

As the main catalyst component in the metathesis 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.

As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable. Such tungsten salt compounds are known to immediately start cationic polymerization when added directly to monomers, which is not preferred. Therefore, the tungsten salt compound is presuspended in an inert solvent such as benzene, toluene, chlorobenzene, etc.
It is preferable to solubilize it by adding a small amount of an alcoholic compound or a phenolic compound before use.

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

Examples include tetrahydrofuran and benzonitrile.

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

On the other hand, the active component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on alkylated metals of Groups 1 to 1 of the periodic table, particularly tetraalkyl tin, alkyl aluminum compounds, and alkyl aluminum halide compounds. Specific examples include diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as active components in the raw material monomer.

The present invention is characterized in that the above-mentioned halogenated paraffin is added to the reactive solution B side.

In this case, as mentioned above, the halogenated paraffin consumes the activator because the different functional groups mixed in during its manufacturing process are reactive with the activator. The key point of the present invention is to discover that the polymerization proceeds quickly and that after the polymerization process is completed, it becomes a stable reactive solution. Therefore, in order to secure the amount of activator necessary for polymerization, This means that it is necessary to add an amount of activator in addition to the amount consumed by .

Therefore, in some cases, it may be possible to initially add a cheaper activator in the corresponding amount to the activator to be consumed, and then add the most suitable activator for use in the polymerization to maximize the economy. You can also take expedient measures.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solution A and solution B, but if the above composition remains unchanged, the polymerization reaction will start very quickly, so the molding Hardening may occur before it flows sufficiently into the casting mold, which often poses a problem, and as mentioned above, it is preferable to use an activity regulator to prevent this problem.

As such regulators, Lewis bases are used, especially ethers, esters, nitrile bases and the like. Specific examples include ethyl benzoate, butyl ether, and diglyme. Although such a regulator can be added to both solutions, it is generally more effective when added to the solution of 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 metathesis polymerization catalyst system 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
In addition, when using alkylaluminum as the active ingredient, the ratio of the aluminum compound to the raw material monomers should be adjusted, excluding any loss due to interaction with the halogenated p-paraffin. from about 100:1 to about 2000:1 on a molar basis, preferably about 200:1
~approximately 500:1 is used. Further, as described above, the masking agent and the regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments.

In practical use, various additives can be added to the polymer molded product produced by the production method of the present invention in order to improve or maintain its properties.

Such additives include fillers, pigments, antioxidants, light stabilizers, other flame retardants, polymer modifiers, and even plasticizers other than halogenated paraffins. Similar to the halogenated paraffin in the present invention, it is impossible to add such additives after the crosslinked polymer is formed, so if they are added, they must be added to the raw material solution described above in advance. There is.

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 this case, it is necessary to add it to either or both of the liquids, but in this case, it does not react with the highly reactive catalyst components or other active agent components in the liquid to a practical extent, and 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 two components are mixed and have a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization, Prefilling is also possible.

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 cylindrical or run couplers can also be suitably used.

Further, it is preferable to add an antioxidant to the polymer molded product produced by the production method of the present invention, and therefore it is desirable to add a phenolic or amine antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-t-butyl-P-cresol, N,N'-
Examples include diphenyl-P-phenylenediamine, tetrakis[methylene(3,5-di-t-butyl-4-hydroxycinnamate)]methane, and the like.

Furthermore, other polymers, especially in the form of a reactive solution, can be added to the polymer molded article produced by the production method of the present invention. As described above, the addition of an elastomer as such a polymer additive is effective in increasing the impact resistance of the molded product and controlling the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene rubber and styrene-butadiene-styrene triblock rubber.

A wide variety of elastomers can be mentioned, such as styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, and ethylene-propylene-genterpolymer nitrile rubber. Furthermore, if a large amount of residual monomer remains in the molded product of the present invention, a characteristic odor may be emitted. As such a residual monomer reducing agent, α
, α.

α-Trichlorotoluene, trichloroacetic acid ester, phthalic acid chloride, benzoic anhydride, phosphorus oxychloride,
Examples include benzenesulfonic acid chloride.

The present invention is carried out by simultaneously carrying out polymerization and molding using the combination of 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, a resin injection method in which a pre-mixed premix is flowed into a mold, and a method in which the catalyst system is It is possible to adopt the RIM method, in which solution A and solution B, which have been separated into two, 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-RIMs, they are easy to release from the mold and often do not require special mold release agents.

In the present invention, since the molded product has many double bonds, an oxidized layer is formed on the surface, and since the halogenated paraffin imparts a certain degree of polarity, it is difficult to adhere to commonly used paints such as epoxy and polyurethane. The properties are good.

Due to the presence of the halogenated paraffin, the molded product thus obtained is plasticized and has improved flexibility compared to a simple metathesis polymer molded product, and in some cases also has improved flame retardancy. As housing for various equipment,
It can be used in a wide range of applications, such as impact-resistant members.

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.

Examples 1 to 3 Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene having a freezing point of 33.4°C.

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

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

[Preparation of main catalyst concentrate] 19.80 g (0.05 mol) of high-purity tungsten hexachloride was added to 90 ml of dry toluene under a nitrogen stream.
- Add butanol 0.925g dissolved in 5ml toluene and stir for 1 hour, then nonylphenol 1
A solution consisting of 1.05 g (0.05 mol) and 5 ml of toluene is added and stirred for 1 hour under nitrogen purge.10
g of acetylacetone is added to the mixture and stirring is continued overnight under a nitrogen purge while purging the by-product hydrogen chloride gas, after which the partially distilled toluene is supplemented to prepare a 0.5M tungsten-containing catalyst concentrate.

[Preparation of activator concentrate] 5.70 g of di-n-octyl aluminum iodide
, ) 31.17 g of raw n-octyl aluminum.

13.42 g of diglyme was mixed under a nitrogen stream, and then DCP was added to dilute to 100 ml in total to obtain an activated concentrate containing 1.0M aluminum.

[Monomer mixture] D CP 96.25 wt%, E N B 3.75
A monomer mixture that maintains a liquid state at room temperature was obtained by mixing wt%.

[Preparation of standard reaction solution A] Place 197 g of the above monomer mixture in a glass bottle with a serum cap, and after purging well with nitrogen, inject 2.96 ml of the main catalyst concentrate with a syringe, stir well, and prepare the standard reaction solution. A solution A was prepared.

[Preparation of standard reactive solution B] Place 197 g of the above monomer mixture in a glass bottle with a serum cap, and after thoroughly purging with nitrogen, pour 4.44 ml of activator concentrate into a syringe and stir well to prepare the standard reactive solution. Prepare B.

[Preparation of reactive solution A containing halogenated paraffin] Put 177 g of the above monomer mixture and 20 g of halogenated paraffin as shown in Table 1 into a glass bottle, stir well under nitrogen purge, and add 2.96 ml of main catalyst concentrate. A halogenated paraffin reactive solution A was prepared by pouring with a syringe and stirring well.

[Preparation of reactive solution B containing halogenated paraffin] 177 g of the above monomer mixture and 201 halogenated paraffin in a glass bottle! and stir well under nitrogen purge.
After thoroughly dispersing the ultramarine blue, add 4.44 m of activator concentrate.
1 was injected with a syringe and mixed well with stirring to prepare a halogenated paraffin reactive solution Bt-.

[Polymerization activity test] 82 ml of a reactive solution heated to 30°C was poured into a test tube fitted with a serum cap and the detection end of a thermocouple was placed at the tip of the test tube under a nitrogen stream using a syringe, and then Similarly, 2 ml of reactive solution A heated to 30°C was added using a syringe, and both solutions were mixed vigorously using a shaker. From the beginning of mixing, polymerization progressed and heat was generated, and the temperature of the indoor bath reached 10°C.
The time until the temperature reaches 0°C is measured as the polymerization time. Furthermore, the amount of reactive solutions A and B added is increased or decreased, and the volume ratio of reactive solution B and reactive solution A and the polymerization time are used as the reactivity evaluation value of the combination of reactive solutions when the polymerization time becomes the shortest. do. In this case, based on the volume ratio and polymerization time of standard reactive solutions A and B, which do not contain halogenated paraffin, the combination of standard solution A and solution B containing halogenated paraffin, solution A containing halogenated paraffin and Standard solution B
By measuring and comparing the volume ratio and polymerization time for the combination of solutions A and B containing halogenated paraffin, we will evaluate the polymerizability due to the addition of halogenated paraffin.

That is, the influence of changes over time can be observed by observing the reactivity of the reactive solution immediately after preparation and after it has been left to stand. Even in the case of a standard reactive solution that does not contain halogenated paraffin, in the case of a small volume experiment using a bottle like this experiment,
Since the polymerization reactivity is low and may deteriorate, the combination of this standard solution was used as a control, and the influence of halogenated paraffin was evaluated based on whether it was worse or not different from the standard solution combination.

The test results are summarized in Table-1.

As can be seen from the results, when halogenated paraffin is added to liquid B, the activator is required to provide the minimum polymerization time, compared to the case where neither A nor B is added as a control.
It can be seen that the minimum polymerization time remains almost the same as in the control case, although it takes a longer time. On the other hand, it was found that the polymerization time increased much faster when halogenated paraffin was added to liquid A, and when halogenated paraffin was added to both liquids, and only when added to liquid B, the reactivity was stable. It can be seen that a combination of reaction solutions is obtained.

Example 4 Dicyclopentadiene, ethylidene norbornene 96
．． 523g of 5/3.5 mixed monomer, Toyoparax A
-50,350 g and 29 cc of the above-mentioned activated death penalty concentrate were mixed to prepare a B solution.

On the other hand, 874 g of a 7mer solution containing dicyclopentadiene, ethylidene norbornene, and ethylene propylene terpolymer (EPT-4070 manufactured by Mitsui Petrochemicals) at polymerization ratios of 93%, 3%, and 4%, respectively, and Ir.
ganox 107618g, the main catalyst concentrate 11j
cc was mixed to obtain liquid A. Make sure that the minimum polymerization time is given when these A and B solutions are mixed and polymerized in approximately equal volumes. Both liquids A and B were molded into a plate with a thickness of 3 mm using an ultra-small RIM machine at mold temperatures of 85°C and 60°C. A light brown durable plate was obtained, and its performance was measured with a flexural modulus of 12490.
Kg-Cm/am, Izotsu impact with notch 58Kg
-cm/Cm, high load heat distortion temperature of 52°C, and residual monomer content of 0.82%.

As a combustion test, I cut this board into strips of 1.5 cm x 12 cm, ignited them horizontally with a burner for 30 seconds, and then looked at the situation, and found that none of the strips were extinguished, with some dripping between 2 cm and 8 cm.

On the other hand, for comparison, we conducted a polymerization test in which the same rubber-dissolving monomer liquid as liquid A was used without using chlorinated paraffin, the activator was reduced by about 40% from the above, and liquids A and B were rapidly mixed. After confirming that the minimum polymerization time was given by the capacity, a 3mm thick plate was molded under the same conditions using an ultra-compact RIM machine, and the performance was measured and the flexural modulus was 15,500 kg.
/cd, notched Izot 45Kg, cm/am,
The high load heat distortion temperature was 97°C, and the residual monomer was 1.7%. The results of a combustion test of this board under the same conditions showed that it was approximately 2.
Burn out at a rate of 7 minutes/10cm.

From this result, due to the plasticizing effect of chlorinated paraffin,
It can be seen that the initial aim has been achieved as the polymer has become more flexible, its flexural modulus and high load HDT have become smaller, and its impact resistance and flame retardancy have improved.

Procedural amendment written spontaneously) August J, 1999 1, Indication of the case Patent application No. 2, Name of the invention Method for producing plasticized polymer molded product and combination of reactive solutions 5, Subject of amendment + 2] Specification Page 27, line 9 [12490Kg・"12490
1 (corrected as ff/ctiJ.

"45 ni 'J.CjI/α'α/α" on page 28, line 3.
I am corrected.

CIII/cm J of [45Ky・

Claims (2)

[Claims] (1) A reactive solution (solution A) of a metathesis polymerizable cycloolefin monomer containing a catalyst component of a metathesis polymerization catalyst system and a reactive solution (solution A) of a metathesis polymerizable cycloolefin monomer containing an activator component of a metathesis polymerization catalyst system. A method for producing a plasticized polymer molded product by mixing at least B) and molding at the same time as polymerization, characterized in that a halogenated paraffin is added to the solution B. (2) A reactive solution (solution A) of a metathesis polymerizable cycloolefin monomer containing a catalyst component of a metathesis polymerization catalyst system and a reactive solution (solution A) of a metathesis polymerizable cycloolefin monomer containing an activator component of a metathesis polymerization catalyst system. A combination of reactive solutions consisting of at least B), characterized in that a halogenated paraffin is added to the solution B.