JPS63215708A - Molded product of crosslinked polymer, manufacture thereof and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To produce the title molded product excellent in heat resistance, releasability and paint adhesion using an inexpensive mold with the polymerization initiation speed controlled, by subjecting a monomer mixture of a metathesis polymerizable cyclic compound containing dicyclopentadiene and a specific carboxylate to bulk polymerization in the presence of a metathesis polymerization catalyst system. CONSTITUTION:A monomer mixture comprising 50-90mol.% one or more metathesis polymerizable cyclic compounds (A) containing 30mol.% or more dicyclopentadiene having a purity of 95% or more and 50-1mol.% at least one (B), as Lewis base, of 1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphth alenecar-boxylate and 1,4-methano-1,4,4a,5,6,7,8,8a-octahydronaphthalenecarbox ylate is subjected to bulk polymerization in the presence of a metathesis polymer ization catalyst system (C), for example, tungsten hexachloride.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a new and improved crosslinked polymer molded product of a cyclopentadiene polymer, a method for producing the same, and a combination of reactive solutions therefor.

More specifically, the present invention relates to a crosslinked polymer molded product obtained by bulk polymerizing monomers containing synchropentadiene using a methanose polymerization catalyst, a method for producing the same, and a combination of reactive solutions used therefor.

b Prior Art Synchropentadiene (hereinafter sometimes abbreviated as 'DCP') is a thermodynamically produced cyclopentadiene which is one of the main components of the C1 fraction used to produce ethylene etc. by Tefsa cracking. It is obtained in the form of a stable dimer and can be said to be an abundant petrochemical raw material.

DCP has conventionally been used as a raw material for obtaining petroleum resins and the like through thermal radical polymerization or cationic polymerization. However, recently, a technique has been developed in which two double bonds in the ring of DCP are subjected to open three-phase polymerization using an olefin metathesis polymerization catalyst system to obtain a molded body of a crosslinked polymer from DCP at once (for example, JP-A-58-129013 (see publication). This technology uses a one-reaction molding method to easily obtain large-sized molded products from the aforementioned abundant petrochemical raw materials, and the molded products have excellent physical properties with a good balance of rigidity and impact resistance. It has industrial value in that it is

By the way, the metathesis polymerization catalyst system used in the above-mentioned reactive method is generally tungsten.

The combination K of a metal salt catalyst such as rhenium or tantalum and an organometallic compound such as aluminum or tin for activating the catalyst exhibits activity as a catalyst system. The above method utilizes this point, and although polymerization does not start when both the catalyst component and the activator component are mixed in separately separated DCP, metathesis can be carried out by rapidly mixing the two components. Polymerization is disclosed, reaction molding proceeds and molded products are obtained all at once.

In such a metathesis polymerization catalyst system, both of the above-mentioned components are highly reactive, and even if the reaction injection molding method described above is used, the reaction rate after mixing the two components is too fast, so that there is insufficient reactivity in the mold. It has been found that there are cases in which gelation begins before pouring and a good product cannot be obtained.

Furthermore, depending on the application, it may be more advantageous to mix the two liquids in a premix state for a certain period of time, then pour it into the mold and heat it to harden, as the equipment is simpler, rather than reaction injection molding. I've come to understand.

On the other hand, the crosslinked polymer obtained by the presence of a metathesis polymerization catalyst system of Dicyc G7/<ntadiene.

It was found that the softening point was 100°C or less, and that the improvement in heat resistance was also an important improvement point. Therefore, the present inventor has conducted intensive research into a method for simultaneously controlling the polymerization initiation rate and improving heat resistance, and has finally arrived at the present invention.

It is known that the activity of a metathesis polymerization catalyst can be adjusted by adding a Lewis space compound. However, when Lewis space is added to adequately control the degree of activation, it remains in the polymer, resulting in problems such as deterioration of the properties of the polymer and generation of volatile components.

C. Structure of the Invention Therefore, the present inventor discovered that if such Lewis space is contained in a monomer having metathesis polymerizability and polymerized together, low molecular weight Lewis space will not remain and the above-mentioned disadvantages will be eliminated. We believed that it would be a win-win situation if such a copolymerized Lewis space group could impart advantageous properties to a polymer, and as a result of our research into such Lewis space group-containing monomers, we arrived at the present invention.

That is, if Lewis space is too strong, the amount of copolymerizable monomers that can be added will be limited, and the amount of residual monomers will increase overall.

Therefore, as Lewis space, we focused on ester groups because they are relatively weak and easy to manufacture, and
The present invention was achieved by discovering that specific carboxylic acid esters having this structure are suitable for this purpose.

The present invention +1 is based on such knowledge and includes the following inventions.

(1) At least t of a metathesis-polymerizable cyclic compound containing at least 30 moles of synchropentadiene
ss O ~ 99 mo/1,%, 114,5.8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene-carboxylic acid esters and hr,4-methano -I H4,4a + 5.6.71818 a-
At least one of octahydronaphthalene-carboxylic acids
A crosslinked polymer molded product obtained by bulk polymerizing a monomer mixture consisting essentially of 50 to 1 mol of seeds in the presence of a metathesis polymerization catalyst system.

(2) In a method for bulk polymerizing a metathesis-polymerizable cyclic compound in the presence of a metathesis polymerization catalyst system to obtain a crosslinked polymer molded product, at least one of the metathesis-polymerizable cyclic compounds containing at least 30 moles of synchropentadiene as a raw material monomer is used. 50 to 99 mol% of one type, and 1
．． 4,5.8-dimethano-1,4,4a,5,6,7,
8,8a-octahydronaphthalene-carboxylic acid esters and 1,4-methano-1,4,4a, 5.6+7.
8.8 A method for producing a crosslinked polymer molded article, characterized in that a monomer mixture consisting essentially of at least 1 m50 to 1 molar of a-octahydronaphthalene carboxylic acid esters is used.

(3) (a) A reactive solution of a metathesis polymerizable cyclic compound containing a catalyst component of a metathesis polymerization catalyst system (solution A)
and (a reactive solution (solution B) of a metathesis-polymerizable cyclic compound containing an activator component for a methane polymerization catalyst system). The composition of the compound is 50 to 99 mol% of at least one metathesis polymerizable cyclic compound containing at least 30 mol of synchropentadiene, and 1,4,5.8-dimethano-11
4+411+5+6+7.8.8a-octahydronaphthalene-carboxylic acid esters and 1.4-meta/
At least one type of 1,4,411,5w6+7t8.8a-octahydronaphthalene-carboxylic acid ester5
A combination of reactive solutions that are monomer mixtures consisting of substantially more than 0-1 mol.

Preferred specific examples of the above-mentioned specific carboxylic acid esters used in the present invention include the following compounds. These are shown using methyl ester as an example, but
It may be a furkyl ester such as the corresponding ethyl ester or a 7-aryl ester such as a phenyl ester.

6.7-bis(methoxycarbonyl) -L4+5+8
-dimethano-1,4y4a,5,6t7+8,8a-octahydronaphthalene ■ 6-(methoxycarbonyl) -1,4,5,8-dimethano-1,4,4a,5,6.7,8,8a- Octahydronaphthalene 6-(methoxycarbonyl)-6-methyl-1t4t5
t8-dimeta/-1,4,4m,5,6,7,8,8
a -Octahydronaphthalene 6,7-bis(methoxycarbonyl) -1,4-methano-1,4,4a,5tL7t8,8aoctahydronaphthalene■ These carboxylic acid esters include, for example, cyclopentadiene and nadic acid diester. , 5-flukoxycarbonylnorbornene or tetrahydrophthalic diester by Diels-Alder reaction.

The raw material carboxylic acid esters used in the present invention must be highly purified. Particular attention must be paid to hydroxyl compounds and carboxyl compounds, which are raw materials before ester hydrolysis or ester formation, as these are both strong catalyst poisons for metathesis polymerization catalysts.

DCP, which is one of the monomers used in the present invention, is preferably highly purified. DC used in the present invention
P has a general 1cDcP purity of 95% or more, more preferably 97% or more, and impurities must naturally not inhibit the activity of the metathesis polymerization catalyst system, but it must have metathesis polymerizability. The content of polar compounds such as alcohols, carboxylic acids, and carbonyl compounds that inhibit metathesis polymerization is preferably as small as possible.

Furthermore, in the present invention, in addition to the above two types of monomers, other metathesis-polymerizable cyclic compounds can be appropriately copolymerized and used at the pressure within the above-mentioned range.

As such compounds, those containing 1 to 2 metathesis polymerizable dichloroflukene groups are generally used. Particularly preferred are those having norbornene type bonds. Hydrocarbons are particularly preferred, and specific examples include dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, 5-vinylnorbornenenorbornene, 5-cyclohexenylnorbornene, 1,4-methanol i+4+4a
t5+L7,8,8a-octahydronaphthalene+
1 + 4 + 5 + 8-dimethano-1,4,4m
.

5.6,7,8,8a-octahydronaphthalene, 6-
Ethylidene-1,4,5,8-dimethano-1,4,4m
, 5,7°8.8a-heptahydronaphthalene, 1
14+5,8-dimethano-1,4,4a,5,8.8a
-hexahydronaphthalene, tricyclo(s l 21
110)) Lysocar 5°11-diene, norbornadiene, ethylene bis(5-norbornene), etc. can be mentioned.

Further, if necessary, a metathesis-polymerizable cyclic compound containing a different element such as oxygen and nitrogen can be used for copolymerization.

Such a copolymerizable polymer preferably has a norbornene structural unit, and the polar group is an ester group,
Ether groups, cyano groups, N-substituted imide groups, etc. are preferred.

Specific examples of such copolymerizable monomers include 5-methoxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, 5-phenypoxymethylnorbornene/, 5-cyanonorbornene,
6-diatu-1,4,5,8-dimethano-1,4,4a
, 5,6,7,8,8a-octahydronaphthalene, N
-Butylnadenic acid imide and the like can be mentioned. As mentioned above, the metathesis-polymerizable cyclic compound for copolymerization is also required to contain as little impurities as possible that would inactivate the metathesis-polymerization catalyst system.

The specific carboxylic acid esters used in the present invention are used in an amount of 50 to 1 mol in the total monomer mixture.
Within this range, the amount can be changed as appropriate depending on the purpose.

That is, the amount of such carboxylic acid esters added is that (
Therefore, it affects the adjustment of the polymerization initiation rate and the softening point of the obtained bomber, and the amount can be adjusted depending on the performance required depending on the application.
Generally, it is often used in a range of 35 to 3 mol.

The other metathesis-polymerizable cyclic compound in the present invention is one in which 30 mol or more of the compound contains DCP.

Generally, DCP is the cheapest monomer in such a monomer, so it is preferable to use a large amount of DCP from a cost standpoint. In general, it is desirable to use at least 50 moles or more, and preferably at least 80 moles in the metathesized monomerizable cyclic compound.

The hexamers other than DCP are generally 30% of the metathesis-polymerizable cyclic compound, if necessary.
Used within the range of moles or less.

The general proportions of the monomer mixture used in the present invention are as described above, but it is necessary to determine the optimum range of each by testing depending on the purpose.

Original E! As is well known, the metathesis polymerization system used to obtain the crosslinked monomer molded product in A generally consists of two components: a main catalyst component and an activator component.

To apply such a catalyst system to bulk polymerization, the activator component is first added to the monomer, then the main catalyst component is added to initiate polymerization, and the molded product is obtained by shaping the monomer before gelation occurs. It is possible to adopt a method in which the main catalyst component and the activator component are added at the same time, a method in which the main catalyst component and the activator component are added at the same time, and a method in which a molded product is obtained in the same manner.

However, the metathesis polymerization reaction is generally an exothermic reaction, and once the polymerization starts, the system is further heated and the reaction is accelerated, and the reaction is completed at an extremely high speed. In the case of 7 j 'J t+, shaping of large finished products is often possible.

Therefore, as mentioned above, two solutions are prepared in advance: a solution consisting mainly of the monomer and the main catalyst component (solution A), and a solution consisting mainly of the monomer activation side component (solution B), and the collision Mixing (RIM method) or a method of rapidly mixing with a static mixer or the like, immediately pouring into a mold, shaping, and then curing in the mold can be suitably used. In that case, it is not necessarily necessary that the monomer composition be the same in both solutions; It can be changed arbitrarily by

For example, when using the function of the carbo/acid ester as a polymerization initiation rate regulator, it is possible to add a large amount to the solution (B), and conversely, it is also possible to add a small amount (by adding it, it does not slow down too much). .

As the catalyst component in the metathesis polymerization catalyst system of the present invention, salts such as tungsten, rhenium titantal molybdenum, etc.) are used, 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. Furthermore, organic ammonium tungstate and the like can also be used.

Such tungsten compounds are known to immediately start cationic polymerization when added directly to monomers in an amount of 1°, which is not preferred. Such tangelsten compounds are therefore prepared in inert solvents such as benzene.

It is preferable to solubilize it by previously suspending L in toluene, chlorobenzene, etc., and 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. Such additives include acetyl 7cetone, acetoacetic acid furkyl esters, and tetrahydrofuran! Examples include benzonitrile. As mentioned above, the carboxylic acid esters used in the present invention are themselves Lewis bases, and often have the effect even without the addition of the above-mentioned compounds.

Thus, the 7-mer solution (solution A) containing the main catalyst component has sufficient stability for practical use.

On the other hand, the activator component in the metathesis polymerization catalyst system is an organometallic compound mainly consisting of alkylated products of metals in Group 1 of the Periodic Table, especially tetraalkyltin! 7/L-Kilfluminicum compound.

Furkylamonium/S-ride compounds are preferred, specifically ilediethylaluminum salt.

Examples include ethylaluminum dichloride, trioctylaluminum, and tetrabutyltin. By dissolving these organometallic compounds as activator components in the mixed monomers, one solution (compatible with solution B) is formed.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solutions A and B, but the specific carboxylic acid esters have a regulating effect on the initiation rate 1 reaction rate. Because of this, it can be cured under stable conditions, but if you want to further adjust the polymerization rate, other Lewis bases can be added.

The amount of the metathesis 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 monomer mixture is about 1,000:1 to about 15,000:1, preferably 2,000:1 on a 1 mol basis.
When an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the monomer mixture is about 100:1 on a 1 mol basis.
~about 2000:1, preferably about 200:1~about 500
A value around 1 to 1 is used. Further, as described above, the masking agent and the regulating agent can be used as appropriate depending on the amount of the catalyst system used through experiments.

In practical use, the crosslinked polymer molded article according to the present invention contains K in order to improve or maintain its properties.

Various mild additives can be incorporated. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers, and the like.

Such additives cannot be added after the crosslinked polymer of the present invention has been molded, so if they are added, they must be added 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 to either or both of the above in advance, but in that case, it is necessary to add the compound to either or both of the liquids, but in this case, it does not react with the highly reactive catalyst component or activator component in the liquid to a practical extent, and It must not inhibit polymerization. In any case, the reaction cannot be avoided, but if the coexistence does not substantially inhibit the polymerization, it can be mixed with the monomer. In addition, in the case of a solid filler, if it is in a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization after one fraction of the components is mixed, it is necessary to , it is also possible to fill it up.

Reinforcements or fillers as additives are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, carbon black, and wollastonite.

Those surface-treated with a so-called silanga puller can also be suitably used.

Further, it is preferable to add an antioxidant to the crosslinked polymer molded product 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-gluo-P-cresol, N,N'-diphenyl-P-phenylenediamine, tetrakis[methylene(
Examples include 3,5-di-t-butyl-4-hydroxycinnamate)]methane.

Furthermore, other polymers can be added to the polymer molded product according to the present invention when it is in the monomer solution state. As such polymer additives, addition of an elastomer is effective in increasing the impact resistance of the molded product and adjusting the viscosity of the solution. Elastomers used for this purpose include:

Styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber,
Polybutadiene, polyisoprene.

A wide variety of elastomers can be mentioned, such as Boolean rubber, ethylene propylene terpolymer, and nitrile rubber.

The polymer molded product of the present invention is produced by simultaneously performing polymerization and molding, as described above.

As mentioned above, such molding methods include the resin injection method, in which a premix of the catalyst system and the monomer mixture is flowed into the mold, and the resin injection method, in which the catalyst system is divided into two parts, solution A and solution B, are poured into the head part. It is possible to use the RIM method, in which the mixture is mixed by collision and poured into a mold as it is. In either case, the injection pressure into the mold can be relatively low, so it is possible to use inexpensive molds.

In addition, the indoor temperature rapidly rises due to the reaction heat generated by the polymerization reaction in the mold, and the polymerization reaction ends in a short time.

Unlike polyurethane-RIMs, they are easily released from molds and often do not require special mold release agents.

The molded product has good adhesion to commonly used paints such as epoxy and polyurethane due to the formation of an oxidized layer on one surface and the polarity of the cyano group.

The molded product thus obtained can be conveniently used in a wide range of applications, mainly large-sized molded products, such as parts for various transportation equipment, including automobiles, and housings for electrical and IT devices.

The present invention will be described in detail with reference to Examples below. Note that the examples are for illustrative purposes only and are not intended to be limiting.

Examples 1-9. Comparative Examples 1 and 2 [Preparation of Raw Materials] Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified synchropentadiene having a freezing point of 33.4°C.

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

On the other hand, commercially available synchropentadiene was thermally dissociated to obtain cyclopentadiene, which was then reacted with 5-methoxycarbonylnorbornene by Die 15-Alder to give 6-(methoxycarbonyl)1 + 4 +
5 + 8-dimethano-1,4,4&,5,6,7,
8,8a-octahyto-naphthalene (MCDMON)
was synthesized.

Similarly, dimethyl nadecate and dimethyl tetrahydrophthalate were each reacted with cyclopentadiene, and 6
,7-bis(methoxycarbonyl)-1,4,5,8
-Dimethano-11414&+5+6+7+8.8a-octahydronaphthalene (DCDMON) and H-6,7-his(methoxycarbonyl) -1,4-methano-1+4
+4a+5+6.7,8,8a-octahydronaphthalene (DCMON) was obtained, respectively.

[Preparation of catalyst component solution]

20g of large tungsten chloride was added to dry toluene 701 under a nitrogen stream, and then a solution consisting of nonylphenol 21JF and toluene 16U' was added to give 0.5 M
A tungsten-containing catalyst solution was prepared, and this solution was purged with nitrogen gas overnight to remove the hydrogen chloride gas purified by the reaction between large tungsten chloride and nonylphenol to obtain a single polymerization catalyst.

Such solution @toe, acetylacetone 1. Mix 500d of Q-1 monomer mixture, tungsten content 0.001
M solution A was prepared.

[Preparation of active north component solution]

trioctylaluminum 85 K to dioctylaluminum iodide 15. A solution B of 0.003M was prepared by mixing diglyme with a molar ratio of 300 parts and adding 500 parts of the monomer as an aluminum content.

The molar ratio of the DCP and copolymer components in the monomer mixture in this solution to the carboxylic acid esters is shown in Table 1 below.
It was shown to.

The above-mentioned solutions were brought to a predetermined temperature such as a catalyst component solution (solution A) and an active agent component solution (solution B) at a temperature of 101/cm, and then the internal pressure was taken out from a syringe which was sufficiently replaced with nitrogen. Both liquids were simultaneously extruded from the syringe at a constant speed into a glass flask equipped with a stirrer under rapid stirring, and after rapid mixing, the stirrer was raised and a thermocouple was inserted, and the temperature was raised to 100°C from the time the liquid was injected from the syringe. The time reached was measured.

Further, the solidified crosslinked resin was taken out, cut into sections, and the softening point was determined using the TMA method in needle penetration mode in a nitrogen stream. The swelling ratio was also measured on another sample. The results are summarized in Table 2 below.

6-(methoxycarbonyl) from mixing temperature and polymerization time
As the content of 1,4,5.8-dimethano-1,4,4a,5,6°7.8,8a-octahydronaphthalene increases, the reaction initiation temperature tends to increase and the reaction time tends to increase. 1 shows that the reaction can be controlled.

Further, in the measurement of the softening point by KTMA, 6-(methoxycarbonyl)-1,4,5,8-dimethano-1,4,4
As the content of a, 5, 6, 7, 8.8 m-octahydronaphthalene increases, the softening temperature is dramatically improved.

This is thought to be because the degree of crosslinking using toluene, which is an indicator of chemical resistance, tends to decrease somewhat as the copolymerization ratio with DCP increases. It can be seen that a composite molded product has been obtained.

The swelling rate is expressed as a weight ratio of the swollen state, with the original weight after immersion in toluene at 30°C - day and night immersion as 1.
did.

For the liquids having the compositions of Examples 6 and 7, liquid A was used.

An ultra-compact RIME that allows each B to be taken out into a syringe, mechanically extruded at a constant speed, guided into a nozzle, mixed by collision, and poured into a mold! When molded in the shade, a brown, durable plate-like product was molded.

Next, 5 d each of the liquids having the compositions of Examples 3 and 4 were taken and stirred under a nitrogen stream to prepare a premix.
When poured into a mold, a similarly durable brown plate was obtained.

Claims (3)

[Claims] (1) At least one metasemis-polymerizable cyclic compound containing at least 30 mol% of synchropentadiene 5
0 to 99 mol% and 1,4,5,8-dimethano-1,4
,4a,5,6,7,8,8a-octahydronaphthalene-carboxylic acid esters and 1,4-methano-1,4
, 4a, 5, 6, 7, 8, 8a-octahydronaphthalene-carboxylic acid esters, a monomer mixture consisting essentially of 50 to 1 mol % of at least one of octahydronaphthalene carboxylic acid esters is bulk polymerized in the presence of a metathesis polymerization catalyst system. A crosslinked polymer molded product obtained by this method. (2) A method for bulk polymerizing a metathesis-polymerizable cyclic compound in the presence of a metathesis polymerization catalyst system to obtain a crosslinked polymer molded product, wherein the metathesis-polymerizable cyclic compound contains at least 30 mol% of synchropentadiene as a raw material monomer. at least one type of 50-9
9 mol% and 1,4,5,8-dimethano-1,4,4a
, 5,6,7,8,8a-octahydronaphthalene-carboxylic acid esters and 1,4-methano-1,4,4a
, 5,6,7,8,8a-octahydronaphthalene-carboxylic acid esters. manufacturing method. (3) (a) A reactive solution of a metathesis polymerizable cyclic compound containing a catalyst component of a metathesis polymerization catalyst system (solution A)
and (b) a reactive solution of a metathesis-polymerizable cyclic compound containing an activator component for a metathesis-polymerization catalyst system (solution B). The composition of the cyclic compound is at least 30 mol% dicyclopentadiene.
50 to 99 mol% of at least one metathesis-polymerizable cyclic compound contained, and 1,4,5,8-dimethano-1,
4,4a,5,6,7,8,8a-octahydronaphthalene-carboxylic acid esters and 1,4,-methanol-1
, 4,4a,5,6,7,8,8a-octahydronaphthalene-carboxylic acid esters50~
A combination of reactive solutions that is a monomer mixture consisting of substantially more than 1 mole percent.