JPH02269759A - Production of polymer molding and combination of reactive solution - Google Patents

Abstract

PURPOSE:To reduce the reaction time and improve the releasability and adhesiveness to a coating material by compounding chlorosulfonated polyethylene into one of two specific reactive solns. of a metathesis-polymerizable monomer, mixing the two solns., and polymerizing and at the same time molding the mixture. CONSTITUTION:A metathesis-polymerizable monomer (e.g. dicyclopentadiene), a major catalyst component (e.g. tungsten hexachloride) of a metathesis polymn. catalyst system, and a solvent are compounded to give a reactive soln. (A). Separately, said metathesis-polymerizable monomer, an activator component (e.g. dioctylaluminum iodine) of said metathesis polymn. catalyst system, and chlorosulfonated polyethylene are compounded to give a reactive soln. (B). The reactive solns. A and B are mixed and poured into a mold wherein the mixture is polymerized and thus molded at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to an improvement in a polymer molded product obtained by simultaneously polymerizing and molding a metathesis-polymerizable monomer in the presence of a metathesis-polymerization catalyst. More specifically, it relates to a method for adding chlorosulfonated polyethylene to improve its properties.

b. Prior Art It is known that strained cyclic olefins undergo ring-opening polymerization using a metathesis polymerization catalyst system. Utilizing this, we utilize monomers such as dicyclopentadiene, which are inexpensively obtained and have two metathesis-polymerizable cyclic olefin groups, because the metathesis polymerization catalyst system consists of two components: a main catalyst and an activator. , a method of mixing component liquids containing each component, quickly pouring into a mold, performing bulk polymerization therein, and performing polymerization and molding in one step was not proposed.
8-129013).

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 are required to have good impact resistance.

As a method of improving the impact resistance of such molded products, a method has been proposed in which a molded product is obtained by adding an elastomer in the form of a reactive monomer solution. It has been found that this can be improved, but it has also been found that the performance changes depending on the type of elastomer added. Therefore, the appropriate elastomer will differ depending on the purpose of use of the polymer molded product.On the contrary, by selecting an appropriate elastomer, products with various characteristics can be obtained, and the polymer characteristics of each elastomer It has become clear that examining the impact on

Therefore, the present inventors focused on chlorosulfonated polyethylene in the process of examining various elastomers. As is well known, this elastomer is made by simultaneously chlorosulfonating and chlorinating polyethylene using sulfuryl chloride, and is abbreviated as C8M in the rubber industry. Are known. By the way, in order to use such an elastomer in a metathesis polymer molded product in which polymerization and molding are performed at the same time as described above, it is necessary to add it in the monomer state before the start of metathesis polymerization, and therefore it is necessary to add it in the monomer state before the start of metathesis polymerization. That is, it must not inhibit the polymerization reaction.

C9 Structure of the Invention Therefore, after examining in detail the presence or absence of such polymerization inhibiting property,
Surprisingly, when added to the liquid containing the activator, which is known to be extremely chemically reactive, a combination of reactive solutions with stable polymerizability is obtained; It has been discovered that a polymer molded product with excellent properties can be obtained by starting the process. This is not because the activator and chlorosulfonated polyethylene have no reactivity, but even if they do react, the reaction ends quickly, so by replenishing the consumed activator, This is because a stable and reactive liquid can be obtained, and in fact, it has been found that more activator is required than in the case where chlorosulfonated polyethylene is not used.

The present invention includes the following inventions.

f) At least a reactive solution of metathesis polymerizable monomers (solution A) containing the main catalyst component of the metathesis polymerization catalyst system and a reactive solution of metathesis polymerizable monomers containing the activator component of the metathesis polymerization catalyst system (solution B). A method for producing a polymer molded product by mixing and molding at the same time as polymerization, characterized in that chlorosulfonated polyethylene is added to the solution B.

(2) a reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B); Become,
A combination of reactive solutions, characterized in that chlorosulfonated polyethylene is added to the solution B.

Chlorosulfonated polyethylene (C
3M) is manufactured by the method described above, and is generally commercially available with a sulfur content of 10.9 to 1.5% and a chlorine content of 20 to 50%, but as mentioned above, it is necessary to dissolve it in a metathesis polymerizable monomer. It is preferable to use commercially available low Mooney viscosity products as so-called solutions for use in the production of rubberized fabrics, etc.

The amount of C8M to be used is determined in an appropriate range from the viewpoint of solubility in the monomer and viscosity of the reactive solution as described above, but generally a range of 2 to 15% is used in liquid B.

The main effect of the addition of C8M is that a molded product with high impact resistance and durability can be obtained, but as a secondary effect,
Since such C8M contains a considerable amount of chlorine, it can have the effect of suppressing the flammability of the polymer molded product to some extent.

A preferred example of the metathesis-polymerizable monomer used in the present invention is dicyclopentadiene.

Tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-phenylnorbornene, 5-ethylidenenorbornene.

Norbornene, norbornadiene, 5-cyclohexenylnorbornene, 1,4,5.8-dimethano-1゜4
, 4a, 5.6.7.8.8.8a-octahydronaphthalene.

1.4-methano-1,4,4a, 5.6.7,8,8.
8a-octahydronaphthalene, 6-nitylidene-1.
4.5.8-dimethano-1,4,4a, 5.6.7.
8.8a-Hebutahydro-naphthalene, 6-methyl-1
,4,5,8-dimethano-1゜4,4a, 5.6.7
．． 8.8a-heptahydronaphthalene, 1458-dimethano-1,4,4a, 5,8.8a-hexahydronaphthalene, ethylenebis(5-norbornene), phenylenebisnorbornene, etc. with 1 to 3 norbornene structures Among them, dicyclopentadiene or a monomer mixture mainly composed of dicyclopentadiene is preferably used.

Furthermore, metathesis-polymerizable 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 and the like.

Such a polar monomer also preferably has 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-methoxyluponylnorbornene, 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, from the viewpoint of solubility in C3M, 5-
Phenylnorbornene, phenylene bisnorbornene,
The solubility can be further increased by using monomers containing benzene nuclei, ester groups, etc., such as 5-methoxycarbonyl-5-methylnorbornene, together with dicyclopentadiene.

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, tungstate salt, 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, it is preferable to use the tungsten salt compound by first suspending it in an inert solvent such as benzene, toluene, or tetralobenzene, and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

Furthermore, 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 to 2 moles of the tungsten compound. Such additives include acetylacetone and alkylnisder acetoacetates.

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 activator component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals from Groups 1 to 2 of the periodic table, particularly tetraalkyltin, alkylaluminum compounds, and alkylaluminum 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 activator components in the raw material monomers.

The present invention is characterized in that C3M as described above is added and dissolved in the reactive solution B. As mentioned above, C3M will probably react with the activator immediately, and in that case, the amount of activator corresponding to the amount of reaction will be consumed, so in order to secure the necessary liter for polymerization, the amount consumed will be added. It is necessary to add the activator in the same amount.

In the present invention, the reaction between the activator and C3M proceeds rapidly,
As described above, this is based on the knowledge that even if carried out in 5 in situ, there will be no adverse effect on the subsequent storage of the reactive solution or the implementation of the polymerization reaction.

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 is often a problem, and as mentioned above, it is preferable to use an activity regulator for this purpose.

As such regulators, Lewis bases are most commonly used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. Although such a regulator can be added to both solutions, it may be more effective to add it to the solution of the organometallic compound activator component. 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 to 1 to 15,000 pairs], preferably 2,000 to 1
In addition, when an alkylaluminium is used as the activator component, the ratio of the aluminum compound to the raw material monomer is about 100:1 on a molar basis, excluding what is lost due to interaction with C3M. ~about 2000:1,
Preferably, a ratio of about 200:1 to about 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 crosslinked 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, flame retardants, plasticizers, and polymer modifiers other than C3M. Similar to C3M in the present invention, it is impossible to add such additives after the crosslinked polymer is molded, but when adding them, it is necessary to add them to the above-mentioned raw material solution in advance. .

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 deactivator component 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 a so-called silane coupler can also be suitably used.

Further, it is preferable that an antioxidant is added to the crosslinked polymer molded product produced by the production method of the present invention, and therefore, it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2.6-t,-butyl-P-cresol, N,
Examples include N'-diphenyl-P-phenylenediamine, tetrakis[methylene(3,5-di-t-butyl-4-hydroxycinnamate)]methane, and the like.

Moreover, the polymer molded product produced by the production method of the present invention is C3M
Other polymers can also be added, especially in the form of reactive solutions. Such polymer additives include, in particular, C3
It may be necessary to add an elastomer to the A liquid side, where it is difficult to add M, in order to adjust the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene rubber, styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, and polyisoprene.

A wide variety of elastomers can be mentioned, including butyl rubber, ethylene propylene diene terpolymer, and 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.

Such residual monomer reducing agents include α, α, α-trichlorotoluene and dicyclodiphenylmethane.

Trichloroacetic acid ester, phthalic acid chloride.

Examples include benzoic anhydride, phosphorus oxychloride, benzenesulfonic acid chloride, and the like.

The present invention is carried out by simultaneously performing 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, which reduces the adhesion to commonly used paints such as epoxy and polyurethane.
In good condition.

(11 Effects) The molded product thus obtained has been improved as described above, and is used as a material for various transportation equipment on land, sea, and on snow, construction materials, mechanical parts in factories, and electronic equipment. It can be used in a wide range of applications, such as members such as housings.

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.

Examples 1-2 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 using 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 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 was added to the mixture, stirring was continued overnight under a nitrogen purge while expelling by-product hydrogen chloride gas, and then the partially distilled toluene was supplemented to prepare a 0.5 M tungsten-containing catalyst concentrate [active Preparation of concentrated liquid of other drugs] D-n-octyl aluminum iodide 5.70 g
, ) 31.17 g of n-octyl aluminum and 13.42 g of diglyme were mixed under a nitrogen stream, and then D
Add CP and dilute to 100 ml in total.
．． An activated concentrate containing 0M aluminum was obtained.

[Monomer mixture] D CP 96.25 wt%, E N B 3.75
% by weight to obtain a monomer mixture that remains liquid at room temperature.

[Preparation of standard reaction solution A] Place 197 g of the above monomer mixture Th 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. B was prepared.

[Preparation of C3M human-reactive solution A] Put 192 g of the above monomer mixture and 5 g of C3M as shown in Table 1 into a glass bottle, stir well under nitrogen purge, and inject 2.96 ml of main catalyst concentrate with a syringe. C8M human-reactive solution A was prepared by stirring.

[Preparation of C8M human-reactive solution B] 192 g of the above monomer mixture and the same C3 in a glass bottle.
After adding 5 g of M and stirring well under a nitrogen purge to disperse the ultramarine blue, 4.44 ml of active agent concentrate was injected with a syringe and mixed with thorough stirring to prepare C3M human-reactive solution B.

[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 2 ml of reactive solution A, also heated to 30°C
was added in the same way with a syringe, and both liquids were mixed vigorously using a mixing machine. From the beginning of mixing, polymerization progressed and heat was generated, and the internal temperature reached 1.
The time until the temperature reaches 00°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, both of which do not contain C3M, the combination of standard solution A and C3M human solution B, C3M human solution A,
By measuring and comparing the volume ratio and polymerization time of the combination of solutions A and B containing C3M and standard solution B, we decided to evaluate the polymerizability due to the addition of C3M.

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. C
Even in the case of a standard reactive solution without 3M, in the case of a small volume experiment using a bottle like this experiment, the polymerization reactivity may be low and deteriorate, so this combination of standard solutions should only be used as a control. , evaluate the effect of C8M addition on whether it is worse or the same.

Summarize the test results in Table 1.

As can be seen from the results, when C3M is added to solution B, more activator is required in order to provide the minimum polymerization time than in the control case where neither A nor B is added. However, it can be seen that the minimum polymerization time remains almost the same as in the control case. On the other hand, it was found that the polymerization time became much faster when C3M was added to liquid A, and when C3M was added to both liquids, and the combination of reaction liquids showed stable reactivity only when added to liquid B. It turns out that can be obtained.

Example 3 35.5 cc of the active agent concentrate was added to 1000 g of a solution in which 74 parts by weight of dicyclopentadiene, 3 parts by weight of ethylidene norbornene, and 3 parts by weight of Toso C5M-2202 were mixed and dissolved to prepare a B solution. On the other hand, for 1000 g of a mixture of 97 parts by weight of dicyclopentadiene and 3 parts by weight of ethylidene norbornene, 0220 g of ethanol
, add 16.2 cc of the above concentrated solution to obtain solution A.

It has been confirmed that both solutions A and B provide the minimum polymerization time when mixed and polymerized in equal volumes. Such A,
Both liquids B were molded into a 3 mm thick plate at a mold temperature of 100°C/80°C using an ultra-small RIM machine. A light brown durable plate was obtained, and its performance was measured to have a flexural modulus of 13,500 kg/cd and a notched izot impact of 45.
Kg-am/cm2, and the high load thermal deformation temperature was 88°C.

On the other hand, for comparison, C3M was not added, and the amount was replaced with dicyclopentadiene and ethylidene norbornene in the same proportion, and the active agent concentrate was reduced to 273.
A plate was made in the same manner using Liquid B, which was confirmed to give the minimum polymerization time at the same volume as the liquid, and the elastic modulus was 15,800.
Kg/cm, Izotsu impact with notch 12Kg -cm
/cm2, and the high load thermal deformation temperature was 92°C. It can be seen that the presence of C3M greatly improves the impact strength.

In addition, when we cut a board into 1.5cm x 12cm strips and conducted a combustion test, the C8M size board was not self-extinguishing and was burnt out, but its burning rate was 30% lower than that of one without additives. It can be seen that the combustibility has decreased to some extent.

Claims (2)

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