JPS6339904A - Novel polymer, its molding and combination of reactive solutions thereof - Google Patents

Abstract

PURPOSE:To obtain a tough polymer excellent in heat and chemical resistances, by polymerizing a monomer based on a 5-alkylidenebicyclo[2,2,1]hept-2-ene in the presence of a metathesis polymerization catalyst. CONSTITUTION:A reactive solution (A) containing a catalyst of a metathesis polymerization catalyst type and a cycloolefinic compound comprising 50 mol% or above 5-alkylidenebicyclo[2,2,1]hept-2-ene of the formula (wherein R1-2 are H or 3C or lower alkyl groups except the case in which they are both hydrogen atom) and 50 mol% or below other metathesis-polymerizable monomers (e.g., dicyclopentadiene) and a reactive solution (B) of said cycloolefinic compound containing an activator for the metathesis polymerization catalyst are prepared separately. Solution A and solution B are poured into a mold at a relatively low pressure and subjected to metathesis polymerization to obtain a polymer of formula II.

Description

Detailed Description of the Invention a. Industrial Application Field The present invention relates to a novel polymer obtained in the presence of a metathesis polymerization catalyst, a molded product thereof industrially advantageously produced, and a reaction for obtaining the same. Regarding the combination of sexual solutions.

More specifically, 5-alkylidenebicyclo[2,2,'
1] Polymerization of a monomer mainly consisting of hept-2-ene (hereinafter sometimes abbreviated as "ABH") using a metathesis polymerization catalyst, preferably by bulk polymerization. This invention relates to a combination of a polymer molded product obtained by simultaneous molding and a reactive solution for forming the same.

b, prior art 5-alkylidenebicyclo[2,2,1]hept-2-
Enes, especially ethylidenebicyclo[2,2,1]hept-2-ene [hereinafter sometimes abbreviated as "ENB"], are the D of cyclopentadiene and butadiene.
1els A A compound obtained by isomerizing 5-vinylbicyclo[2,2,1]hept-2-ene, which is a 1der adduct, and has been awarded as the third component for ethylene propylene rubber. Seven polymers of suitable purity are commercially available for use in polymerization.

Therefore, in order to obtain a new polymer using this compound, the inventors of the present invention have conducted extensive research and have come up with the idea of applying a metathesis polymerization catalyst system. Metathesis polymerization is known to open a cyclic olefin at a double bond to produce a polymer having an olefin in its main chain. However, when metathesis polymerization is applied to ABH, the problem that can be easily predicted is that in addition to cyclic olefins, chain olefins are naturally involved in the metathesis reaction. However, in that case, it is expected that not only crosslinking will occur, but also that it will act as a terminal terminator for polymerization, produce short-chain olefins, and cause undesirable side-effect reactions. In fact, 5-vinylbicyclo[2,2,1]hept-
When metathesis polymerization is applied to 2-ene alone,
This is thought to be due to the a1 reaction, but it has been found that a soft and weak polymer containing a large number of irregular gas pores can only be obtained and is of little practical use.

However, according to research by the present inventors, in the case of A However, it has been discovered that this on-chain double viscosity hardly participates in metathesis polymerization, and a very durable high polymer can be easily obtained, and the present invention has been achieved.

C6 The structure of the invention, that is, the present invention is to obtain a new polymer from ABH by using a metathesis polymerization catalyst.

As mentioned above, metathesis polymerization of ABH is carried out like solution polymerization,
If the reaction is subsequently carried out under mild conditions, the chain double bonds will hardly take part in the reaction and a mostly chain polymer can be obtained.

However, when such a polymer is heated and molded by melt molding or the like, the remaining double bonds often cause a crosslinking reaction and the polymer cannot exhibit sufficient moldability.

Therefore, we have found that it is advantageous to perform bulk polymerization, pour the liquid monomer as it is into a mold, and simultaneously perform the polymerization in one step to obtain a molded polymer product all at once.

In this case, since the metathesis polymerization reaction occurs at a very high speed, polymerization occurs between the time the catalyst components are mixed and the time it is poured into the mold, making injection into the mold difficult in many cases. , it is possible to prepare the main catalyst component and other active agent components of the metathesis catalyst system as separate monomer solutions, and to mix these two components at high speed during injection, collision mixing, or static mixer, and then pour them into a mold. understood. In bulk polymerization, a violent exothermic reaction causes the polymerization system to
Due to the high temperature, some of the chain double bonds will inevitably participate in the reaction, and the resulting polymer will become a crosslinked polymer, but since the molding has been completed, it will not be resistant. It has also been found that a method in which crosslinking is present is rather advantageous to some extent from the viewpoint of chemical properties, heat resistance, etc.

Furthermore, by replacing a part of ASH with other metathesis-polymerizable monomers, not only can a polymer be obtained without any problem, but depending on the selection of the copolymer, in addition to the characteristics of the polymer, It has also been found that other properties can also be imparted.

The present invention has been achieved based on this knowledge, and includes:
It includes the following inventions (1) to (3).

(1) Metathesis polymerization of monomers containing at least half the mole of 5-alkylidenebicyclo[2,2,1]hept-2-ene, with the remainder being substantially larger than other meta-cis polymerizable monomers A new polymer obtained by polymerization in the presence of a catalyst.

(containing at least a majority molar amount of 215-alkylidenebicyclo[2,2,1]hept-2-ene and, if necessary, the remainder being substantially more than other meta-cis polymerizable monomers) as a metathesis polymerization catalyst. A polymerized molded product obtained by bulk polymerization in the presence of a polymer and molding at the same time as the polymerization.

[3] At least a, a reactive solution of a cyclic olefin compound containing a metathesis polymerization catalyst system catalyst (solution A), and b, a reactive solution of a cyclic olefin compound containing an activator of a metathesis polymerization catalyst system (solution B). In the combination of reactive solutions that react by mixing, the cyclic olefin compounds in solution A and solution B have a combined composition of at least 5-alkylidenebicyclo[2,2,1]hept-2-ene. 1. A reactive solution combination characterized in that it contains monomers in a majority molar amount, with the remainder being substantially more than other meta-cis polymerizable monomers, if necessary.

ABH used in the present invention is represented by the following general formula [I] (wherein, R+ and R2 are hydrogen atoms or war damage prime number 3).
Represents the following alkyl group, provided that both are not hydrogen atoms at the same time. ) Preferably, R+ and R2 are both methyl groups, and one of R+ and R2 is a methyl group and the other is hydrogen.

That is, 5-isopropylidenebicyclo[2,2,1]hept-2-ene (hereinafter abbreviated as "PNB"), 5
-ethylidene[2,2,1]hept-2m'n (ENB
) is preferred, and the latter is particularly preferred.

The ABH used in the present invention generally has an ABH purity of 95%.
The above content is preferably 97% or more, and the impurities should naturally not inhibit the activity of the metathesis catalyst system, but preferably should 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.

In the present invention, at least one other meta-cis-polymerizable monomer can be copolymerized and used in an amount that does not exceed the molar amount of ABH used. In general, we do not teach anything as long as it has sufficient metathesis polymerizability.

Such copolymerized monomers are easily mixed in during the monomer manufacturing process of ABH, and it is difficult to remove them by force.
Although it includes those that can be used as they are to make monomer synthesis advantageous, in general, those that can impart new properties and characteristics to the polymer of the present invention are preferred. Such copolymerizable monomers include those that contain two or more metathesis-polymerizable groups in one molecule and have the effect of increasing the degree of crosslinking of the resulting polymer, and those that have organic Lewis space polar groups that are polymerizable for metathesis. It is preferable to use plastic that can improve chemical resistance and heat resistance by adjusting the polymerization rate or introducing polar groups into the molecular chain.

Such copolymerization components include hydrocarbon cycloalkenes such as dicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dibase, 5-vinylnorbornene, 5-isopropenylnorbornene, norbornene, and 5-phenylnorbornene; -cyanofulbornene,
Examples include cycloalkenes containing different elements such as 5-alkoxycarbonylnorbornenes, 5-methyl-5-alkoxycarbonylnorbornenes, and N-alkylnadic acid imide.

Dicyclopentadiene is a hydrocarbon.

Particularly preferred copolymerization components of the 5-gonylnorbornene heteroelement-containing monomer include 5-cyanonorbornene, 5-alkoxycarbonylnorbornenes, and 5-methyl-5-alkoxycarbonylnorbornenes.

The amount of the copolymer component to be used relative to ΔBH can be arbitrarily used depending on the requirements, as long as it does not exceed the molar amount of 88H used, but is preferably 5 to 45 mol%.
Particularly preferably, it can be used in a range of 10 to 40 mol%.

As is well known, a metathesis polymerization catalyst system generally consists of two components: a main catalyst component and an active agent component.

Therefore, for metathesis polymerization, it acts as a difunctional 2
When carrying out the polymerization using a combination of seven polymers, it is possible to perform the polymerization under mild conditions in the coexistence of an inert solvent to obtain a polymer that is mostly chain-like.
In this case, if you try to melt and mold it further, it may cause gelation, so as mentioned above, it may be more advantageous to carry out bulk polymerization and perform molding at the same time as the polymerization. many. In this case, the polymerization proceeds at an accelerated rate due to the generated polymerization heat, and the humidity of the molded product rises considerably, so that even in the case of ABH alone, it is inevitable that some crosslinking will occur. However, as mentioned above, when attempting to obtain a molded product, it is often more advantageous in terms of solvent resistance and heat resistance if crosslinking occurs to some extent.

For such bulk polymerization, there is a method in which an active agent component is first added to a monomer, and then a main catalyst component is added, and the polymerization is started and the product is shaped until gelation occurs to obtain a crosslinked molded product. It is also possible to add the main catalyst component and the other active agent components to the monomer mixture simultaneously to obtain a crosslinked product.

However, metathesis polymerization reactions are generally exothermic reactions, and once the polymerization starts, the system is heated further and the reaction speeds up, completing the reaction at a very high rate. It is often difficult to form a gelling agent using the methods described above.

Therefore, as mentioned above, two solutions, a solution containing the main catalyst component of the metathesis catalyst (solution A) and a solution containing other active agent components (solution B), are prepared in advance and mixed by collision. (RIM method) or a method in which the mixture is rapidly mixed using a static mixer or the like, immediately poured into a mold, shaped, and then hardened within the mold can be suitably applied.

In this case, the monomer composition does not necessarily need to be the same in both liquids, and can be arbitrarily changed as long as the overall monomer composition is within the above range.

Regarding the method for producing molded products using a two-component mixing method using metathesis polymerization, a method for producing molded products using dicyclopentadiene as a monomer is described in JP-A No. 58-12901.
It is disclosed in Publication No. 3.

Salts such as halides such as tungsten, rhenium, and tantalum are used as catalyst components in the metathesis polymerization catalyst system in the above-described molding method, and tungsten compounds are particularly preferred. As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable. Such tungsten compounds are known to immediately start cationic polymerization if added to ABHs immediately after, which is not preferable. Such tungsten compounds are therefore prepared in inert solvents such as benzene.

It is preferable to use it by suspending it in advance in toluene, chlorobenzene, etc., and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

In general, it is preferable to add a tungsten compound or a chelating agent to prevent undesirable polymerization as described above. Such additives include acetylacene,
Acetoacetic acid alkyl esters, tetrahydrofuran,
Examples include benzonitrile. By doing so, the monomer female solution (corresponding to solution A) containing the tungsten compound will have sufficient stability when used in practical use.

On the other hand, the activation inhibitor 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. Specifically, diethylaluminum chloride,
Examples include ethylaluminum dichloride, trioctylaluminum, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as activator components in ABHD or ABH-containing mixed monomers.

In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solution A and solution B, but the polymerization reaction starts very quickly with the above composition, so the molding is difficult. Hardening may occur before it has sufficiently flowed 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, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, diglyme, etc. Such regulators are generally added to the solution of the organometallic compound activator component.

For example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the above monomer is about 100 m on a molar basis.
0:1 to about 15,000:1, preferably around 2,000:1, and when an alkyl aluminum is used as the active inhibitor component, the ratio of the aluminum compound to the 11M compound is about 100:1 on a molar basis. 1 to about 200
A ratio of around 0:1, preferably about 200:1 to about 500:1 is used. Furthermore, as for the masking agent and the regulating agent as described above, it is possible to use them in an amount of 1ml as appropriate depending on the usage of the catalyst system according to experiments.

In practical use, various additives can be added to the cross-linked polymer molded article according to the present invention in order to improve or maintain its properties. Such additives include fillers, pigments, antioxidants, light stabilizers.

Examples include 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 raw material solution described above in advance.

In this case, an easy method is to use the solution A and solution B.
One method is to add it to either or both of them in advance, but in that case, it is impossible to add it after the crosslinked polymer of the present invention has been molded. It is necessary to add the raw material solution described above 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 be something that does not inhibit polymerization.
It won't happen. 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,
It is also possible to fill a mold with a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or while the two components are mixed together.

Reinforcing materials or fillers as additives are effective in improving the bending modulus. Examples of such materials include glass fiber, mica, carbon black, and wollastonite. Those surface-treated with so-called silane gobbler 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 phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2.6-
t-Butyl-P-cresol, N,N'-diphenyl-P-phenylenediamine, tetrakis[methylene(
3,5-di-tert-butyl-4-hydroxycinnamate)]methane, methylene-4,4'-bis(3,5-di-
Heapylphenol), etc.

Furthermore, 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 styrene-butadiene-styrene triblock rubber,
Styrene-isopress, polyisoprene, butyl rubber.

A wide range of elastomers can be mentioned, including ethylene propylene diene terpolymers.

As described above, the polymer molded article of the present invention is preferably manufactured by simultaneously carrying out polymerization and molding, and therefore is preferably manufactured by the so-called RIM method. In molding using the RIM method, as mentioned above, monomer solutions (that is, solutions A and B) in which the catalyst component and the active agent component are dissolved separately are rapidly mixed in the mixing head of the RIM group, and then the mold is molded. A common method is to obtain a molded product by polymerizing and molding the resin.

The injection pressure into the mold can be relatively low, thus making it possible to use inexpensive molds.

The injection pressure into the mold can be relatively low, and therefore an inexpensive mold can be used. Also,
When the polymerization reaction inside the mold starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike polyurethane-RIM, it is easy to release from the mold and often does not require a special mold release agent.

The molded product has surface polarity, 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.

It can be confirmed from the reaction characteristics of metathesis polymerization and the infrared absorption spectrum of the resulting polymer that the polymer of the present invention mainly consists of the following structure [I[].

)+2CC...[■CoH-CH3 It is also possible to raise the softening point by post-heat treatment or the like by utilizing the reactivity of the chain alkene in the side chain remaining in the polymer.

Therefore, this is a very industrially advantageous combination of a polymer molded product and a reactive solution.

The molded products thus obtained can be used in a wide range of applications, mainly large molded products, such as parts for various transportation devices including automobiles, and housings for electrical and electronic 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 limited thereto.

Example 1-6 Commercially available 5-ethylidenebicyclo[2,2,1]hebdo-2-ene (ENB) was distilled and purified under a nitrogen stream to obtain a product with a purity of 98.5% or more as determined by gas chromatography. I got something.

Similarly, commercially available dicyclopentadiene (DCP) was distilled to obtain a purified product without lowering its freezing point to 33.4°C.

[Preparation of catalyst component solution] 209 tungsten hexachloride was added to 70 m of dry toluene under a nitrogen stream, and then a solution consisting of 21 g of nonylphenol and 16 d of toluene was added to prepare a 0.5 M tungsten-containing catalyst solution. The solution was purged with nitrogen gas overnight to remove the hydrogen chloride gas generated by the reaction between tungsten hexachloride and nonylphenol, thereby obtaining a polymerization catalyst.

10d of such solution, acetylacetone 1. Od mixed sugar 500IIIi! The tungsten content is 0. OQ
A 1M solution A was prepared.

[Preparation of active ingredient solution] Diethylaluminum chloride 0.189. A 0.003M solution B was prepared by mixing 0.375d of isopropyl ether and 500m of mixed monomer to prepare the aluminum content.

The compositions of the monomers used to prepare both solutions A and B are as follows.

The above solution was mixed with 10 m of catalyst component solution (solution A) and 10 m of activator component solution (solution B) at an internal temperature of 25°C.
It was then taken out into a syringe that had been thoroughly replaced with nitrogen. The syringe was extruded at a constant speed, a liquid was injected, the liquid was mixed in a nozzle, and the mixture was applied to an ultra-compact RIM machine that can be poured into a mold to obtain a plate-shaped, extremely durable three-dimensional polymer molded product.

The time at which heat generation in the system suddenly starts after the solutions are mixed and the maximum temperature reached in the system are indicators for determining whether polymerization has been carried out without being inhibited. In the range of 1 to 6, they generally show similar values (slightly more ENB tends to be higher), and all show high polymerizability.

Furthermore, in the table, the softening point using TMA and the swelling ratio using toluene, which are indicators of heat resistance and chemical resistance, were measured.

Table: Softening Point and Swelling Rate The swelling rate is quite large, probably because the ENB homopolymer has the smallest degree of crosslinking, but it becomes smaller as the copolymerization ratio of DCP is increased.

In addition, at the softening point by TMA, N
When the softening point of the sample heated in 2 was reduced again, the softening point became considerably higher in all cases, and especially in Example 5, the apparent softening point was no longer observed, indicating the possibility of improving the softening point by post-treatment. There is.

Example 7 [Preparation of catalyst liquid component liquid] Tungsten hexachloride 209 was added to 70 d of dry toluene under a nitrogen stream, and then a solution consisting of nonylphenol 219 and toluene 16- was added to prepare a 0.5M tungsten-containing catalyst. Prepare the solution 1. This solution was purged with nitrogen gas overnight to remove hydrogen chloride gas generated by the reaction between tungsten hexachloride and nonylphenol, which was then used as a polymerization catalyst.

Mix 1.0 d of such solution and 0.10 m acetylacetone ENB9. Mixed with Od 1 no., tungsten content 0.0
A 5M solution was prepared.

[Preparation of active inhibitor component solution ($i) 0.18 g of diethylaluminum chloride and 9.5 m of ENB mixed with 0.375 d of isopropyl ether were mixed to prepare a 0.15 M solution as the aluminum component.

Dry toluene (moisture content 51) 1 in a 100 d glass container
)Ill) 50 dl was added and nitrogen bubbled to sufficiently replace the gas in the container and solution, and the internal temperature was maintained at 25°C.

A gel-like material was obtained by adding 2 d of the active agent component solution and 2 Mm of the catalyst component solution in this order and stirring vigorously.

This gel-like material was further dissolved in toluene Sod, cast on a glass plate, and dried to obtain a transparent and strong film.

[Brief explanation of drawings]

The attached drawing shows the infrared absorption spectrum of ENB homopolymer.

Claims (3)

[Claims] (1) A monomer containing at least a majority molar amount of 5-alkylidenebicyclo[2,2,1]hept-2-ene and, if necessary, the remainder being substantially larger than other metathesis polymerizable monomers, is added to the metathesis polymerization catalyst. A new polymer obtained by polymerization in the presence of (2) A monomer containing at least a majority molar amount of 5-alkylidenebicyclo[2,2,1]hept-2-ene and, if necessary, the remainder being substantially larger than other metathesis polymerizable monomers, is added to the metathesis polymerization catalyst. A polymer molded product obtained by bulk polymerization in the presence of a polymer and molding at the same time as polymerization. (3) a, a reactive solution of a cyclic olefin compound containing a metathesis polymerization catalyst system catalyst (solution A), b, a reactive solution of a cyclic olefin compound containing an activator of a metathesis polymerization catalyst system (solution B), at least In the combination of reactive solutions that react by mixing, the cyclic olefin compounds in solution A and solution B have a combined composition of at least 5-alkylidenebicyclo[2,2,1]hept-2-ene. 1. A reactive solution combination characterized in that it contains monomers in a majority molar amount, with the remainder being substantially more than other metathesis-polymerizable monomers, if necessary.