JPH01163212A - Metathetic polymer of cyclic olefin - Google Patents

Abstract

PURPOSE:To obtain the title novel high-molecular weight polymer having excellent strength, providing a reaction molded article having excellent mold release characteristics and adhesivity to coating compounds, by blending a specific cyclic olefin with a metathetic polymer. CONSTITUTION:The aimed polymer consisting of a repeating unit selected from repeating units shown by formulas I and II (R1 and R2 are H or <=3C alkyl with the proviso that R1 and R2 are not simultaneously H) or a different repeating unit derived from the unit and a monomer copolymerizable into a metathetic polymer. The polymer is obtained by polymerizing a compound shown by formula III (m is 0 or 1) or polymerizing a mixture of the compound shown by the formula III and another metathetic copolymerizable monomer in the presence of a metathetic polymerization catalyst. The compound shown by formula III is preferably 5-ethylidenebicyclo[2,2,1]hept-2-ene when m is 0 and 6-ethylidene-1,4,5,8-dimethanol-1,4,4a,5,7,8,8a-heptahydronaphthalene when m is 1.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to metasense polymerization of cyclic olefins, new polymers, molded articles from the polymers, and hand-processable compositions for producing 1q of polymers.

b. Prior art Cross-linking of a cyclic olefin having a norbornene unit, such as dicyclopentadiene (hereinafter sometimes abbreviated as "DCP"), having an olefin group in its main chain in the presence of a metalhesis polymerization catalyst system. It is known to produce polymers (see JP-A-58-1290i3). In this known technique, large-sized moldings of cross-linked polymers can be easily produced by the reaction molding method of DCP. This molding has rigidity. It is industrially valuable because it has excellent physical properties with a good balance of impact resistance and impact resistance. (hereinafter sometimes abbreviated as "A B H") can be used industrially.

For example, 5-ethylidene-bicyclo[2,2,2-heptoe-2-ene (hereinafter sometimes abbreviated as 'ENB') is the D of cyclopentadiene and butadiene.
5-vinylbicyclo[2,2,1]hept-2-ene (hereinafter referred to as “■B
It is a compound obtained by the isomerization of ethylene-propylene rubber (sometimes abbreviated as "H"), and is prized as a third component for ethylene-propylene rubber, and is commercially available in a purity that can be used as a monomer for ionic polymerization. ing.

Furthermore, the D of cycloheptadiene to ABH mentioned above
6 represented by the following formula by iels-Alder addition
-alkylidene-1,4,5,8-dimethano-1,4゜4a, 5.7.8.8a-hebutahydronaphthalene (
Hereinafter, this may be abbreviated as "AD HN").

As is clear from the above chemical formula, both ABH and ADTOIN have one chain olefin in addition to one cyclic olefin.

It is known that chain olefins, when added to a metasense polymerization system using cyclic olefins, act as end-terminators in the polymerization, produce short-chain olefins, and cause undesirable side reactions.

Therefore, when ABH and ADHN are used in metasense polymerization, it is naturally expected that the presence of the chain olefin will act as an end-stopper in metasense polymerization, resulting in relatively low molecular weight crosslinked metasense polymers and volatile byproducts. be done.

In fact, 5-methylidenebicyclo[2,2,heptohept-2-ene (hereinafter sometimes abbreviated as "MBH'") corresponding to R'=R"=H in the above formula is a metasense polymerization catalyst. In the presence of , a crosslinked polymer is produced. [Paul
R, Hein J, Polymer Sci.

Polym, Chem, 11.167 (1973)
].

After) As mentioned in Comparative Examples 2 and 3 of the book, the inventor has
Metasense polymerization was carried out with H and MBH individually, but both yielded insoluble polymers that were soft, brittle, and had numerous irregular pores. This clearly shows that the pendant chain olefin acts as a terminal capping agent or terminal transfer agent in the metasense polymerization reaction.

In contrast, we have found that ENB, a typical ABH example, is hard and strong, and upon metasense polymerization produces a soluble polymer with virtually no gas pores. VBH of ENB in this metasense polymerization
This action different from that of MBH and MBH was completely unexpected since the structures of these three are very similar. E
The difference between NB and VBH is simply the difference in the position of the chain olefin, and the difference between ENB and MBt-( is that ENB is MB
The only difference is that the methylidene group of H is replaced with a methyl group. After all, MBH-t)VBH also has a pendant linear α-olefin, but ENB has 3 internal double bonds.
Substituted with two hydrocarbons.

Therefore, the above-described difference in the effect of ENB in metasense polymerization is explained by the fact that the chain double bond of ENB does not substantially participate in metasense polymerization due to steric hindrance.

The present inventor has proposed that ENB and cyclohebutadiene Diets-
6-ethylidene-1,4,5,8-dimethano-1,4,4a,5゜7,8.8a-heptahydronaphthalene (hereinafter referred to as ``E DHN''), which is a typical Alder adduct of ADHN. It was also found that ABH and A
Like EBN and EDHN, D'HN can also be used to obtain useful molded products by reaction molding.

Particularly when these are used together with other metasense polymerizable monomers such as DCP, particularly excellent reaction molding methods and molded products can be obtained as described below.

The inventors found that when ABH and/or ADHN are used as monomers for at least a portion of the metasense polymerization, the linear double bond of ABH or ADHN is substituted with at least three hydrocarbon groups. Therefore, it was discovered that it cannot participate in metasense polymerization and does not inhibit the reaction. Ring-opening polymerization of norbornene-type cyclic olefins also produces high molecular weight, strong polymers with pendant chain double bonds.

The inventors have discovered that ABH and/or ADHN can be effectively used as part of the reaction molding monomers in conjunction with metasense polymerizable monomers such as DCP.

The object of the present invention is to provide a new polymer by metasense polymerization of ABH or ADHN. A further object of the present invention is to provide useful molded products from the polymer. Another object of the invention is to provide a method for providing the new polymer and the useful moldings. A further object of the present invention is to provide polymerizable compositions that yield new polymers by metasense polymerization.

C9 Structure of the Invention The object of the present invention is to obtain a novel polymer consisting of at least one repeating unit selected from the following general formula and at least one different polymer derived from at least one repeating unit and one or more metasense coelectrizable monomers. The present invention relates to a novel polymer consisting of repeating units and a molded article formed from the polymer.

Further, the present invention provides a method for polymerizing a compound having at least one compound of the following general formula (III) or by polymerizing a mixture of the compound and at least one other metasense coelectrizable monomer in the presence of a metasense polymerization catalyst system. The present invention relates to a method for producing the above-mentioned novel polymer by.

Further, in the present invention, at least two of a first reaction liquid containing a catalyst component of a metasense polymerization catalyst system and a cycloolefin and a second reaction liquid containing an activator component of a metasense polymerization catalyst system and a cycloolefin are mixed, and then In the method for obtaining a molded article by supplying this mixture to a mold and causing a polymerization reaction, at least one compound of general formula (III) is used as the cycloolefin, or at least one metasense coelectrizable monomer of the compound and at least one compound is used as the cycloolefin. This is an improved method by using a mixture.

The present invention further provides a plurality of polymeric compositions containing at least one compound of general formula (I[I), or a mixture of said compound and at least one other metasense copolymerizable polymer, and a catalyst component. The catalyst component and the activator component of the metasense catalyst system comprising the activator component provide multiple parts of the polymerizable composition that are not mixed in the same solution.

In the above general formula (II[), when m is O, the compound corresponds to ABH and provides a repeating unit of the above general formula (I>).When ■ is 1, the compound is ADHN
and provides a repeating unit of general formula (II) above.

Among the compounds represented by the above general formula (III), AB
H is represented by the general formula (I[Ia).

It is particularly preferred that both R1 and R2 are methyl groups, or that one of R1 and R2 is a methyl group and the other is hydrogen. Zunawara, 5-isopropylidene bicyclo[2,2
, 5-edylidene bicyclo[2
, 2, hepto-2-ene (ENB) is preferred, the latter being particularly preferred.

ADTOIN is represented by the general formula (Ib).

It is particularly preferred that R1 and R2 are both single methyl groups, or that one of R1 and R2 is a methyl group and the other is a hydrogen atom.

That is, 6-itupropylidene-1,4,5.8-dimethano-1,4,4a,5,7,8.8a-hebutahydronaphthalene (hereinafter sometimes abbreviated as "P D HN ") ) and 6-ethylidene-1,4,5,8-dimethano-1°4,4a,5.7.8.8a-hebutahydronaphthalene (EDHN) are preferred, with the latter being more preferred.

A B H and ADHN used in the present invention have a purity of 9
5% or more is preferable. And more preferably 97% or more. It is desirable that the catalyst does not contain impurities or inhibit the activity of the metasense catalyst system, and preferably has metasense polymerizability. The content of polar compounds that inhibit metasense polymerization, such as alcohols, carboxylic acids, and carbonyl compounds, is preferably as low as possible.

In the present invention, at least one other metasense polymerizable monomer can be copolymerized with A B H and ADHN in any proportion.

In general, any polymer may be used as a copolymerizable polymer as long as it has sufficient metasense polymerizability.

Cyclobutene from the viewpoint of metasense polymerizability.

Cycloalkenes other than cyclohexene are used, such as cyclopentene, cycloheptene, cyclooctene and substituted derivatives thereof. A compound having at least one norbornene structure represented by the general formula (IV>) in the molecule is preferred.

Preferred examples of such copolymerizable polymers include A B
Contains metasense polymerizable by-products and/or unreacted raw materials in the H or A D HN manufacturing process. In particular, the use of such by-products and residual substances as additives in copolymerization may lead to ABH and ADl-IN.
It is advantageous when it is difficult to remove from the polymer and/or when it imparts excellent physical properties to the polymer.

As an example of such a copolymerizable polymer, in the case of EDHN, which is a typical and most preferred example of ADHN, EN
B, DCP, tricyclopentadiene, oligocyclopentadiene having three or more cyclopentadiene units, and compounds represented by the following formulas.

ENB is the starting material. DCP is also a starting material when used as a raw material for cyclopentadiene, and a by-product when cyclopentadiene is used as a starting material.

All of the above compounds have metasense monomerism like EDHN. The use of such copolymerizable polymers is particularly advantageous when EDHN is used in reaction molding. ENB, VBH and DCP correspond to the above copolymerization agents.

As mentioned earlier, the vinyl group of VBH inhibits metasense polymerization. However, if the content of VBH is low,
For example, when the amount is 5 to 10%, a polymer with satisfactory performance can be obtained.

Preferred examples of the copolymerizable monomer for providing the polymer in the present invention include two or more metasense polymerizable groups such as a norbornene structure or a sterically strained cyclopentene ring in one molecule, and the resulting polymer Items that have the effect of increasing the degree of crosslinking (8) have organic Lewis space polar groups that adjust the rate of metasense polymerization or introduce polar groups into the molecular chain to improve chemical resistance and heat resistance. Preferred are lacquer (B) and the like which improve the properties.

Examples of (A) include dicyclopentadiene, oligocyclopentadiene having at least three cyclopentadiene units, 1,4,5,8-dimethano-1,4
,4a,5,8.8a-hexahydronaphthalene.

tricyclo-[2,2,1,Ol trideca-5,11
-Dienes and the like are preferred.

Examples of 4* property 1 (B) of Lewis space are cyano group,
Mention may be made of carboxylic acid ester groups, ether groups and tert-amine and/or amide groups such as pyridine.

Examples of Lewis space (B) include 5-cyano-norbornene, 5-6-dicyaznorbornene, 6-diatu-1
．． 4,5.8-dimethano-1,4,4a, 5.6.7
゜8.8a-Octahydronaphthalene, 5-methoxy-
Carbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornenebornene, 5-phenoxymethylnorbornene.

Examples include 5-acetyl-oxydinorbornene, 5-methylbutoxyluponylnorbornene, nadic acid dimethyl ester, and 5-norbornenylcarboxylic acid L5-(4-pyridyl)norbornene.

Further, examples of norbornene derivatives having one metasense polymerizable group include 5-butylnorbornene, 5-isopropenylnorbornene, 5-phenylnorbornene, cyclopentadiene-methylcyclopentadiene codimer, 1,4,5 .8-dimethano-1. 4.
4a, 5, 6, 7, 8. 8a-octahydronaphthalene can be mentioned.

Among the above-mentioned copolymerizable polymers, in particular, dicyclopentadiene, tricyclopentadiene having two or more cyclopentadiene units in one molecule, 5-cyanonorbornene,
5-Phenylnorbornene.

Oligocyclopentadiene such as 5-alkoxycarbonylnortyl-alkoxycarbonylnorbornene and 5-pyridylnorbornene are preferred.

Such a copolymer component is used in an amount of 0 to 99 mol %, particularly 0 to 95 mol %, based on ABH and ADHN.

Compounds of general formula (III), mixtures of said compounds with other metasense coelectrizable monomers consisting essentially of repeating units of general formula (I), repeating units of general formula (II), general formula (I) and/or novel polymers produced by metasense polymerization of repeating units of general formula (II> and those derived from other metasense coelectrifying monomers) are identified by infrared absorption spectroscopy or other methods.

\ / 1-IC-C)-1
(I)/ Since the polymer of the present invention has a post-reactive chain double bond, it is possible to improve the softening point by post-curing or the like. Furthermore, the presence of the chain double bond group makes it possible to add chemical treatments to polymers and molded articles.

In particular, the metasense polymer made from ADHN has a much higher T( ) than the metasense polymer made from DCP. Therefore, ADHN is effective as a copolymerizable monomer in increasing the Tg of other metasense polymers.

ADHN is effective when used in proportions as low as 5 mole percent. Therefore, ADHN can be effectively used with other copolymerizable polymers in a wide range of proportions.

As a result, other copolymerizable monomers A D l-(
2 to 50 mol% to change the properties of the N polymer;
In particular, it can be used in a range of 5 to 50 mol%, more preferably 5 to 45 mol%.

On the other hand, when ADHN is used to enhance the 19 of other metasense polymerizable polymers, such as DCP polymers, it is used in a proportion of 5 to 50 mol %, especially 5 to 40 mol %, with other polymers.
, more preferably 10 to 40 mol %.

A B )-1, Special 4.1: E N B Part a <
When copolymerizing with a metasense coelectrizable monomer such as DCP, the residual tumer decreases and the softening point of the polymer increases, resulting in improved heat resistance.

Furthermore, when ABH or ADHN is added to a reaction solution consisting of a norbornene cyclic olefin such as dicyclopentadiene, the freezing point of the reaction solution is lowered, preventing assimilation at room temperature. This makes handling such as mixing the reaction solution and injection into a mold easier.

The metasense catalyst system is highly reactive and easily reacts with not only oxygen and water but also other polar components in the monomer and loses its activity. Therefore, when dicyclopentadiene is used in polymerization in the presence of a metasense catalyst system, it is used in particularly high purity. Although the freezing point tends to be slightly lowered by dissolving the catalyst component in the polymerization-reactive solution, it is generally 20'C or higher. The metasense catalyst system has high reactivity, and if kept at a temperature of 30° C. or higher, the activity will decrease in a short time even if the catalyst and activator are added separately into separate solutions. It is difficult to store the reaction solution at high temperatures so that it can be used immediately. However, since the reaction solution is in the form of a solution when used, it should be heated to dissolve it before use.

Therefore, the reaction solution must be humidified immediately before the polymerization reaction, which is troublesome. In order to overcome this drawback, it becomes possible to add a composition that does not inhibit the activity of the catalyst system and does not lower the freezing point of dicyclopentadiene.

However, if the composition remains unpolymerized in a crosslinked polymer molded product, various problems such as deterioration of the physical properties of the molded product occur.

In contrast, the present invention provides A B in dicyclopentadiene.
By adding H or ADHN, the freezing point of the polymerizable solution is lowered, making it possible to easily handle it. Furthermore, as mentioned above, ABl-1 and ADHN are highly metasense polymerizable and copolymerized with other metasense polymerizable monomers such as dicyclopentadiene, so the resulting copolymer has no odor from the residual monomers. can be reduced. ENB, as already mentioned, is commercially available and is particularly suitable for this purpose.

As mentioned above, ASH and/or ADHN can be present in an amount of 0 to 50 mole% of other metasense polymerizable polymers to modify the properties of the polymer while preserving its properties.
, especially 2 to 50 mol%, more preferably 5 to 45 mol%
Can be copolymerized.

Additionally, ABH and/or ADHN may be present in 1 to 50 mol% with other metasense polymerizable monomers such as DCP.
It can be used as a monomer for copolymerization within the range of .

In order to improve heat resistance and/or post-curing properties, copolymers containing 5 to 50 mol%, especially 10 to 40 mol% of ABN and/or ADHN are preferred.

In order to lower the freezing point of the reaction solution, 1 to 15 mol%, especially 1
It is suitable to add ~10 mol % of ABH and/or AD)-IN, especially ABH, as an upper layer for copolymerization. DCP or a mixture of DCP and oligocyclopentadiene (mainly tricyclopentadiene) and/or a codimer of cyclopentadiene-methyl-cyclopentadiene are the most preferred metasense polymerizable monomers.

As a particularly preferred embodiment, composition (i) comprises 1 to 10 mol% ENB, 99 to 80 mol% DCP, and 0 to 10 mol%
mol % of the aforementioned metasense polymerizable monomer (tricyclopentadiene is the best) and composition (11) is 5-50
Mol% EDHN, 95-20mol% DCP and 0
~40 mol % of the other metasense polymerizable monomers mentioned above (tricyclopentadiene being the best).

As is generally known, the metasense polymerization catalyst system consists of two components: a catalyst component and an activator component. AB
When the metasense combination of H or ADHN is carried out under mild conditions such as solution polymerization in an inert solution,
Polymers that are soluble and melt-formable (which means substantially linear) can be obtained. This is because the chain double bond group in ABH or ADFIN does not substantially participate in the metasense reaction as described above.

However, moldability, particularly melt moldability, is undesirable because it easily causes polymerization of double bonds remaining in the metasense polymer, which easily gels upon oxidative dimerization and/or heating.

Therefore, the monomer solution is injected into the mold in bulk.
It is advantageous to carry out the polymerization reaction in situ.

This bulk polymerization can be carried out by first adding an activator component to the monomer, then adding a catalyst component to start the polymerization, and finally molding before solidification to obtain a crosslinked product, or by adding a catalyst component to the monomer. and the activator component can be added simultaneously to the seven-mer mixture and then moldings can be obtained in the same manner as described above.

Since the metasense polymerization reaction is an exothermic reaction and the reaction proceeds very quickly, the polymerization reaction may occur before the solution is poured into the mold, making it difficult to pour the solution into the mold.

Therefore, it is desirable to separate the reaction stock solution to be injected into the mold into several parts. In other words, it is desirable to separately add the catalyst and activator of the metasense polymerization catalyst system to separate seven-mer solutions, and then separate them. The other reaction solutions are quickly mixed by impingement mixing (RIM method) or a static mixer and then poured into a mold. The polymer formed in this polymerization tends to contain some crosslinked structure. This is a rapid exothermic reaction that increases the temperature of the polymerization medium,
This is because side chain double bonds are involved in side reactions. However, some degree of crosslinking is preferred since it imparts chemical and heat resistance to the molded article. In this method, the monomer is contained in at least one reaction liquid, one reaction liquid contains the catalyst component, and the other reaction liquid contains the activator. It is not necessary to equalize the proportions of the monomers in the eight liquids. The proportions of the monomer pairs can be freely changed as long as the proportions of the monomers are within the above-mentioned range.

JP-A-58-129013 discloses such a molding method using a two-liquid heating method containing dicyclopentadiene as a monomer.

Salts such as halides of tungsten, molybdenum, rhenium, tantalum, etc. are used as catalyst components in the metasense polymerization catalyst system produced by the above-described molding method. Particularly preferred are tungsten compounds. As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable. More specifically, tungsten hexachloride and tungsten oxychloride are preferred. It is known that when such a tungsten compound is directly added to ABH or ADHN, cationic polymerization starts immediately, which is not preferable. Therefore, it is preferable to use such a tungsten compound by first suspending it in an inert solvent such as benzene, toluene, chlorobenbin, etc., and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound. Furthermore, it is preferable to add a Lewis base or a chelating agent to prevent undesired polymerization as described above. Such an additive is acetylacetone.

Acetoacetic acid alkyl esters, tetradidrofuran,
Examples include benzonitrile.

By doing so, the solution containing tungsten and other main catalyst components for metasense polymerization (corresponding to solution A) will have sufficient stability when used in practical use.

On the other hand, the activator component in the metasense polymerization catalyst system is preferably an organometallic compound mainly containing alkyl compounds of metals from Groups 1 to 2 of the periodic table, particularly tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds. Specifically, diethylaluminum chloride, ethylaluminum dichloride, and trioctylaluminum.

Examples include dioctylaluminum iodide and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as activator components in the ABH- or ADHN-containing mixture alone.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solution A and solution B, but if the composition is kept as it is, 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 for this reason it is preferable to use an activity modifier.

As such regulators, Lewis bases are generally used, especially ethers, esters, and nitriles. Specific examples include ethyl benzoate, butyl ether, diglyme, and benzonitrile. Such a regulator is generally used by being added to the side of the solution (solution B) of the components of the organometallic compound activator.

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 above monomer is about 10 on a molar basis.
00:1 to about 15,000:1, preferably 2,000:1
In addition, when an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the above monomer is about 100:1 to about 200 on a molar basis.
A ratio of around 0:1, preferably 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 used through experiments.

In practical use, various additives may be added to the crosslinked polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers, reinforcing agents, pigments, and antioxidants.

These include light stabilizers and polymer modifiers. 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. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it is also possible to mix it with the monomer to prepare a third liquid and use it immediately before polymerization. . In addition, in the case of a solid filler,
If both components are mixed and the shape is such that the voids can be sufficiently filled immediately before starting the polymerization reaction or during polymerization, it is also possible to fill the mold.

Reinforcers or fillers as additives are effective in improving the flexural modulus. Such materials include glass fiber, mica, and carbon black.

You can defeat Wolastonite, etc. these,
Those surface-treated with a so-called silane coupler can also be suitably used.

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

In addition, other polymers can be added to the polymer molded article according to the present invention when it is in a monomer solution state. As such polymer additives, the addition of elastomers is effective in increasing the impact resistance of the molded product and in controlling the viscosity of the solution. Elastomers used for this purpose include a wide range of elastomers such as styrene-butadiene rubber, butadiene-styrene triblock rubber, ethylene-propylene rubber, polybutadiene, polyisoprene, butyl rubber, and ethylene-propylene-diene terpolymer.

The polymer molded article of the present invention is preferably produced by simultaneously carrying out polymerization and molding, as described above.

Therefore, it is preferable to manufacture by the so-called RIM method. In RIM molding, as mentioned above, monomer solutions (that is, solutions A and B) in which the catalyst component and the deactivator component are dissolved separately are rapidly mixed in the mixing head of the RIM machine, and then molded into a mold. A common method is to obtain a molded product by injecting the resin into a polymer, polymerizing and molding it.

The injection pressure into the mold can be relatively low, thus 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 easily released from molds and often do not require special mold release agents.

The molded product has a polar surface, probably due to the formation of an oxidized layer on the surface, and has good adhesion to commonly used paints such as epoxy and polyurethane.

The molded product thus obtained can be used for automobiles, motorbikes,
It can be used in a wide range of applications, mainly in large molded products, such as parts for various transportation equipment such as motor boats and snowboats, and housings for electrical and electronic equipment.

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 limited thereto.

Examples 1-13. Comparative Example 1 Commercially available dicyclopentadiene was distilled under reduced pressure under a nitrogen stream,
Purified dicyclopentadiene (D) with a freezing point of 33.4°C
CP> (q). The purity was 99% or higher when measured by gas chromatography. Commercially available 5-ethylidene bicyclo [2,2,2,2,2,2,2,2,2,2,2,2,2,2,2,2,2-heptot-2-ene (ENB) was purified by distillation, and the purity was determined by gas chromatography. 99.5% or more was obtained.

5-ethylidenebicyclo[2,2,2,2, 2, 2, 3] In order to examine the effect of lowering the melting point by heptose-2-ene (ENB), ENB was added in an amount of 2.5 mol% and 5 mol%, respectively, based on DCP.

When mixed monomer liquids were prepared with 10 mol% concentration and the freezing points of each were measured, the results were as shown in the table below, and it was found that the freezing point decreased in proportion to the amount added.

Table 1 Freezing point depression [Preparation of catalyst component solution] Tungsten hexachloride 20C1 was added to 70ml of dry toluene under a nitrogen stream, and then nonylphenol 21 (
A tungsten-containing catalyst solution of 0.58 was prepared by adding a solution consisting of 16rIIl of tungsten hexachloride and 16rIIl of toluene, and the solution was purged with nitrogen gas overnight to obtain tungsten chloride purified by the reaction of tungsten hexachloride with nonylphenol. Hydrogen gas was removed to prepare a polymerization catalyst.

ioml of such solution, 1.0 rrdl of acetylacetone
Mix 500 m of n-monomer and tungsten-containing ff1
0.001) 1 Solution A was prepared.

[Preparation of Activated Subcomponent Solution] 0.181 J of diethylaluminium chloride, 0.375 J of isopropyl ether and 500 J of mixed monomer were mixed to prepare a 0.003 M solution B as the aluminum content.

When the prepared solution was kept at 25°C, both the activator component solution and the catalyst component solution were frozen in the solution prepared from pure dicyclopentadiene only, but the solutions made from mixed monomers remained in solution state. was maintained.

Further, although the mixed monomer solution corresponding to Example 3 was stored in a refrigerator with an internal temperature of 7° C., neither solution was frozen. It can be seen that the effect of lowering the freezing point has appeared, making it extremely easy to use in practical use.

Furthermore, ENB content is 20 mol% (Example 4), 30 mol%
(Example 5), 40 mol% (Example 6), 48 mol% (
Example 7), 50.5 mol% (Example 8), 60 mol%
(Example 9), 70 mol% (Example 10).

80 mol% (Example 11), 90 mol% (Example 12)
, and 100 mol% (Example 13) of the mixed m-isomer were used to prepare solutions A and B.

The above solution was taken out into a syringe which had been kept at an internal temperature of 25°C and sufficiently filled with nitrogen. Ultra-compact R that can extrude at a constant speed, inject liquid, mix it in the nozzle, and pour it into the mold.
An extremely durable three-dimensional polymer molded product in the form of a plate was obtained using an IM machine.

After mixing the solutions, the time at which heat generation in the system suddenly starts, the time at which the temperature in the system reaches 100°C (hereinafter referred to as the start time), and the maximum temperature reached in the system are determined by the time at which polymerization is inhibited. This is an index to judge whether or not the metasense synthesis is carried out without any oxidation, but as the proportion of ENB increases, the initiation time tends to be shorter and the maximum temperature reached tends to be higher, indicating that the metasense smallness of ENB is high. There is.

The residual monomer base is extracted by immersing 1 g of solid polymer in 50 ml of toluene for 48 hours or more, and is measured by gas chromatography. As the results are summarized in Table 2, the residual ENB is so small that it can hardly be detected when 30% or less ENB is used in the mixed solution of DCP and ENB, and the residual DCP is almost undetectable when the DCP homopolymer is used. Compared to that, when ENB is added, it is smaller in all ranges.

This reduction in small amounts of residual monomer significantly reduces odor, which is a significant drawback with DCP polymer moldings.

Furthermore, the softening point by TMA method and swelling ratio using toluene, which are indicators of heat resistance and chemical resistance, were measured, and the results are summarized in Table 2. Swelling rate is pure DC
Compared to the case where P is used, the copolymerization ratio of ENB tends to increase as the copolymerization ratio increases. This indicates that ENB does not create crosslinks and produces a linear polymer.

On the other hand, the softening point of the plate formed by TMA method is also 2 in nitrogen atmosphere.
After raising the temperature to 80°C, the softening point is measured again, and it becomes slightly higher. In particular, as in Examples 5 and 9, the apparent softening point was no longer observed, indicating the possibility of improving the softening point by post-treatment using the ENB component.

Example 14 [Preparation of catalyst component solution] 20 g of tungsten hexachloride was added to 70 d of dry toluene under a nitrogen stream, and then a solution consisting of 21 (l) of nonylphenol and 167 liters of toluene was added to give a solution of 0.51 g of tungsten hexachloride.
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 tungsten hexachloride and nonylphenol, thereby obtaining a polymerization catalyst.

Such solution i, o y, acetylacetone 0.10 mf
! and ENB9.0mff were mixed to prepare a solution with a tungsten content of 0°05N.

[Preparation of active inhibitor component solution] Diethylaluminum chloride o,iag, isopropyl ether 0.375 m! Mixed monomers and EN
B9.5d is mixed to give an aluminum content of 0.15
A solution of H was prepared.

50 d of toluene (moisture content: 5 ppm) was placed in a 100 ml glass container, and the gas in the container and solution was completely replaced by bubbling with nitrogen at 25°C. 2 ml of deactivator solution and 27 ml of catalyst solution! were added in this order, and the mixture was vigorously stirred to obtain a gel-like substance.

This gel-like material was dissolved by adding 50 d of toluene. This indicates that the pendant double bond groups of the ENB polymer do not participate in the metasense reaction, do not form crosslinks, and have a substantially linear structure. The solution is cast onto a glass plate and dried to produce a transparent and strong homopolymer of ENB through metasense polymerization.

The infrared absorption spectrum of ENB homopolymer is shown in FIG.

Examples 15-24 Commercially available 5-ethylidene bicyclo[2,2, hepto2
-Ene (ENB) and dicyclopentadiene were subjected to a Diels Alder reaction at 170'C in an autoclave, and then purified by distillation under a nitrogen stream to obtain ADHN 8 with a purity of 99% or more as determined by gas chromatography.

Similarly, commercially available dicyclopentadiene (DCP) was distilled to obtain a purified product having a freezing point of 33.4°C.

A catalyst solution was prepared from tungsten hexachloride and nonylphenol in the same manner as in Examples 1 to 13.

Such a catalyst solution 1 (7!, acedelace+one 1.Od.

E D HN or EDHN/DCP mixture 500
m was mixed to prepare a tungsten-containing i0.001M solution A.

Diethylaluminium chloride o,iag, isopropyl ether 0.375%, EDHN or ED to I
Mix the N/DCP mixture liquid to obtain an aluminum content of 0.
．． Solution B of 0038 was prepared.

The compositions of the monomers used to prepare both solutions A and B are shown in Table 3. The above solution was converted into catalyst component solution (solution A) 1
07! Activator component solution (solution B) i.

ml was taken out into two syringes which were maintained at an internal temperature of 25°C and replaced with nitrogen sufficiently. The molded plate was subjected to RIM molding in the same manner as in Examples 1 to 13 to obtain a very strong plate-shaped molded product.

Table 3 shows the temperature during mixing, start time; time to reach 100°C, TMA softening point, and swelling rate.

The TMA softening point and swelling rate were measured in the same manner as in Examples 1-13.

The results in Table 3 show that the polymerization times in Examples 15 to 24 were almost the same, and that all of the Examples had high polymerizability.

When measuring the softening point using TMA, the softening temperature increases dramatically as the EDHN content increases.

First, the copolymerized polymers with DCP containing 90 to 50 mol% of EDHN (Examples 16 to 20) have higher softening points than the polymer containing EDHN alone (Example 15).

When the softening point of the sample heated to 280'C in N2 is measured again, the softening point becomes higher.

In particular, in Examples 19, 22, 23, and 24, no apparent softening point was observed, indicating the possibility of improving the softening point by post-treatment. The swelling ratio tends to decrease somewhat as the copolymerization ratio of DCP increases.

Example 25 Preparation of U catalyst liquid component solution] 20p of tungsten hexachloride was added to 70d of dry toluene under a nitrogen stream, and then a solution consisting of 21g of nonylphenol and 167g of toluene was added to prepare a tungsten-containing catalyst solution of 0.58%. was prepared, and this solution was purged with nitrogen gas overnight to remove the hydrogen chloride gas produced by the reaction between tungsten hexachloride and nonylphenol, which was used as a polymerization catalyst.

Such solutions i, o y, acedelacetone o, iom1
i combined EDHN9. Mix Oml, tungsten content 0
．． A 05M solution was prepared.

[Preparation of activator component solution] 0.18 g of diethylaluminium chloride was mixed with isopropyl ether to give an aluminum content of 0.18 g. 15) A solution of 1 was prepared. 50 parts of dry toluene (moisture content: 5 Dpm) was placed in a 100 m glass container, and nitrogen bubbles were applied to the container to sufficiently replace the gas in the container and the solution, and the internal temperature was maintained at 25°C.

Activator component solution 2f12. A gel-like material was obtained by adding catalyst component solution 2Ir11 in this order and stirring vigorously.

This gel-like material was further dissolved in 50 d of toluene, and after being chelested on a glass plate, it was dried to obtain a transparent and strong film.

This indicates that the pendant double bond groups of the polymer obtained from ED-IN do not participate in the metasense reaction, do not have a crosslinked structure, and are substantially linear.

The infrared absorption spectrum of EDHN homopolymer is shown in FIG.

Example 26 DCP and EBN were reacted at 170°C in an autoclave to obtain EDHN. Tricyclopentadiene, a by-product, was separated by distillation from unreacted DCP and EDHN. pentagen 10
Example 15 A mixed solution of 60% by weight and DCP
Reaction molding was carried out in the same manner as in 24. The resulting polymer had a TMA softening point of 142°C.

Example 27 Solution A with a rubbery 100% mixture consisting of 5.7% styrene-butadiene rubber containing 28.3% EDHN, 66% DCP, 0% styrene and 5% styrene.
and B were created.

Solution A was 0,001 as shown in the previous example.
)t tungsten catalyst. Solution B contains trioctylaluminum and dioctylaluminum iodide.
Containing 0.003 tof aluminum activator component and 0.0 diglyme as activity modifier in a molecular ratio of 5=1
It consists of 03M.

These two reaction solutions were put into the day-tanks of a reaction injection molding machine (lance type, manufactured by Niigata Tekkosho Co., Ltd.), and
At a pressure of K (J/Cm2, the temperature is 7.
By reaction injection molding solution A and solution B into a mold kept at 0°C, 500mm x 500mm with a thickness of 3mm was formed.
A square polymer plate was fabricated. The created board is shown in Table 4.
It has well-balanced properties of hardness, impact strength, and heat resistance as shown in .

Table 4 Properties of reaction injection molded plate made of EDHN and DCP co-polymer
m2) Initial notched isot strength (23°C) 35Kgcm/cm (0'C
) 29K(ICm/Cm(-30'C) 19
K (1cm/cm after 7 days at 90℃ in air (23℃) 20Kgcm/cm bending strength (
23°C) 627 g/cm2 flexural modulus (2
3°C>17600Ka/cm2 Examples 28-34 Cyclopentadiene and alkyl-phenyl-ether,
Acrylonitrile, methyl acrylate.

Methyl methacrylate, methylcyclopentadiene,
DielS-Atde of styrene, 4-vinylpyridine
5-phenoxymethylnorbornene (PM
NB), 5-cyanonorbornene, 5-methoxycarbonylnorbornene-methyl-5-methoxycarbonylnorbornene (MM
CN), methyldicyclopentadiene (MDCP), 5
-Phenylnorbornene (PNB) and 5-(4-pyridyl)norbornene (PDN) are produced, respectively.

The above monomers were combined with ENB, EDHN and DCP in Table 5.
As a result of mixing the compositions shown in and polymerizing them using the same reaction molding method as in Examples 1 to 13, a strongly crosslinkable polymer plate was obtained. Temperature during mixing, initial time, maximum temperature reached, TMA
The softening points are summarized in Table 5.

It can be seen that the use of monomers with polar groups such as nitriles, esters, ethers and tert-amines increases the initial time. If the initial time is long, it is suitable for molding large molded products.

Comparative Examples 2-3 Commercially available V B H and M B H (Aldrich)
Purify by distillation. Purified V B H and MBH were found to have a purity of 99% or higher by gas chromatography.

Each of these monomers was polymerized in the same manner as described in Example 3.

The initiation of metasense polymerization occurred similarly, and the maximum temperature reached exceeded 170°C. However, during the polymerization reaction, volatile substances are violently released from the reaction solution, and the resulting polymer is soft.
It was brittle and had many holes. These polymerization properties are significantly different from those of EBN and ED)-IN described in Examples.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the ENB homopolymer obtained in Example 14. Figure 2 shows 6-ethylidene-1,4 obtained in Example 25.
,5,8-dimethano-1,4,4a, 5.7.8.8
1 shows an infrared absorption spectrum of a homopolymer of a-hexahydronaphthalene. % TRANSMITTANCE

Claims (29)

[Claims] (1) A novel polymer comprising at least one repeating unit selected from the following general formula, and a novel polymer comprising at least one repeating unit and at least one different repeating unit derived from one or more metasense copolymerizable monomers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [Here, R_1 and R_2 each represent a hydrogen atom or an alkyl group containing up to three carbon atoms. And R_1 and R_2 are never both hydrogen atoms. ] (2) The first type where R_1 is a methyl group and R_2 is a hydrogen atom
Polymers described in Section. (3) The metasense-polymerizable copolymerizable monomer is a cycloalkene having at least one norbornene structure and, optionally, at least one group selected from other metasense-polymerizable cyclic olefin units and organic polar groups. Polymer according to item 1. (4) Cycloalkenes in which the cycloalkene has one norbornene structure, cycloalkenes having one norbornene structure and one sterically strained metasense polymerizable cyclopentene ring, one norbornene structure, a cyano group, and an ester ethers, tert-
4. The polymer according to item 3, comprising a cycloalkene selected from cycloalkenes having one or two polar groups selected from the group consisting of amines and amide groups. (5) The polymer according to item 3, wherein the cycloalkene is a cycloalkene selected from oligocyclopentadiene and methylcyclopentadiene-cyclopentadiene codimer containing two or more cyclopentadiene units in the molecule. (6) The cycloalkene is dicyclopentadiene, 5-
Phenylnorbornene, 5-cyanonorbornene, 5-
5. The polymer according to claim 4, which is a cycloalkene selected from the group consisting of alkoxycarbonylnorbornene, 5-methylalkoxy-carbonylnorbornene, and 5-pyridylnorbornene. (7) The polymer according to item 6, wherein the cycloalkene is dicyclopentadiene. (8) The polymer according to item 1, comprising repeating units of general formula (I) and repeating units derived from dicyclopentadiene. (9) The polymer according to item 8, wherein in general formula (I), R_1 is a methyl group and R_2 is a hydrogen atom. (10) The polymer according to item 1, comprising a repeating unit of general formula (II) and a repeating unit derived from dicyclopentadiene. (11) In general formula (II), R_1 is a methyl group, R_
11. The polymer according to item 10, wherein 2 is a hydrogen atom. (12) The polymer according to item 1, which contains 100 to 1 mol % of repeating units of general formula (I) or (II) and 0 to 99 mol % of different repeating units. (13) The polymer according to item 12, which contains 100 to 50 mol% of repeating units of general formula (I) or (II) and 0 to 50 mol% of repeating units different therefrom. (14) The polymer according to item 13, which contains 98 to 50 mol% of repeating units of general formula (I) or (II) and 2 to 50 mol% of repeating units different therefrom. (15) The polymer according to item 12, which contains 1 to 50 mol % of repeating units of general formula (I) or (II) and 99 to 50 mol % of different repeating units. (16) The polymer according to item 15, which contains 5 to 50 mol % of repeating units of general formula (I) or (II) and 95 to 50 mol % of different repeating units. (17) Contains 1 to 10 mol% of repeating units of general formula (I) and 99 to 10% of repeating units different from that
16. Polymer according to item 15 containing 90 mol%. (18) Containing 1 to 10 mol% of repeating units of general formula (I), 99 to 80 mol% of repeating units derived from dicyclopentadiene, and repeating units derived from other metasense polymerizable monomers 0 to 1
18. The polymer according to item 17, containing 0 mol%. (19) The polymer according to item 18, wherein R_1 is a methyl group, R_2 is a hydrogen atom, and the other metasense polymerizable monomer is oligocyclopentadiene. (20) Contains 5 to 50 mol% of repeating units of general formula (II), 95 to 20 mol% of repeating units derived from dicyclopentadiene, and repeating units derived from other metasense polymerizable monomers 17. The polymer according to item 16, containing from 0 to 40 mol% such that the total amount is 100 mol%. (21) The polymer according to item 20, wherein R_1 is a methyl group, R_2 is a hydrogen atom, and the other metasense polymerizable monomer is tricyclopentadiene. (22) The polymer according to item 1, which consists essentially of repeating units of general formula (I). (23) The polymer according to item 1, which consists essentially of repeating units of general formula (II). (24) By polymerizing a compound having at least one compound of the following general formula (III), or by polymerizing a mixture of the compound and at least one other metasense copolymerizable monomer in the presence of a metasense polymerization catalyst system. A new polymer consisting of at least one repeating unit selected from the following general formulas (I) and (II), and at least one different repeating unit derived from at least one repeating unit and one or more metasense copolymerizable monomers. A method for producing a new polymer consisting of units. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [Here, R_1 and R_2 each represent a hydrogen atom or an alkyl group containing up to three carbon atoms. And R_1 and R_2 are never both hydrogen atoms. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [Here, m is 0 or 1, and R_1 and R_2 are the same groups as defined in general formulas (I) and (II), respectively. ] (25) The method according to item 24, wherein the metasense polymerization catalyst system comprises a catalyst and an activator. (26) The production method according to item 25, which comprises supplying the catalyst and the activator individually as separate liquids. (27) A plurality of parts of a polymerizable composition containing at least one compound of the following general formula (III) or a mixture of the compound and at least one other metasense copolymerizable monomer, including a catalyst component and an activator component. The catalyst component and the activator component of a metasense polymerization catalyst system comprising a plurality of parts of a polymerizable composition are not mixed in the same solution. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [Here, m is 0 or 1, and R_1 and R_2 each represent a hydrogen atom or an alkyl group containing up to three carbon atoms. And R_1 and R_2 are never both hydrogen atoms. ] (28) The composition according to item 27, wherein the first reaction solution contains the catalyst and the compound or the mixture, and the second reaction solution contains the activator and the compound or the mixture. (29) Mix at least two of the first reaction liquid containing the catalyst component of the metasense polymerization catalyst system and cycloolefin and the second reaction liquid containing the activator component of the metasense polymerization catalyst system and cycloolefin, and then In the method of supplying the mixture to a mold and causing a polymerization reaction to obtain a molded article, at least one compound of the general formula (III) or a mixture of the compound and at least one other metasense copolymerizable monomer is used as the cycloolefin. Improvement method used. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [Here, m is 0 or 1, and R_1 and R_2 each represent a hydrogen atom or an alkyl group containing up to three carbon atoms. And R_1 and R_2 are never both hydrogen atoms. ]