JPS6392625A - Crosslinked polymer molding, its production and combination of reactive solutions - Google Patents

Abstract

PURPOSE:To obtain the title molding excellent in heat resistance and suitable as a large molding such as an automobile member, by simultaneously performing polymerization and molding of a monomer feed comprising a specified adduct or its mixture with other metathesis-polymerizable monomers in the presence of a metathesis polymerization catalyst system. CONSTITUTION:A monomer feed (A) comprising a 1:1 adduct of formulas II and III, formed by performing a Diels-Alder reaction of 3a,4,7,7a- tetrahydroindene (a) of formula I with cyclopentadiene (b) or its mixture with 0-95mol% at least one metathesis-polymerizable monomer selected from among a cycloalkene except cyclohexene, a compound having at least a norbornene skeleton of formula IV (wherein the dotted valence bonds may be combined together through other atoms to form cyclic structures, etc.) is bulk-polymerized in a mold in the presence of a metathesis polymerization catalyst system (B) comprising a base catalyst component (e.g., WCl6) and an activator component [e.g., (C2H5)2AlCl] to perform polymerization and molding simultaneously.

Description

Detailed Description of the Invention a. Industrial Field of Application The present invention relates to the production of a novel cross-linked a polymer molded product with excellent heat resistance obtained by metathesis polymerization, and the production of the molded product that can be produced industrially advantageously. The present invention relates to a method and a combination of reaction solutions for obtaining the same.

More specifically, the Diels-Alder (3&, 4+717&-tetrahydroindene and cyclopentadiene)
To obtain a new cross-linked composite molded product using a metathesis polymerization catalyst system, using a meta-cis polymerizable monomer having a one-to-one adduct as an essential component by the Dials-Alder) reaction, which is also preferably a bulk 1 The present invention relates to a method for simultaneously performing polymerization and molding to obtain a C crosslinked polymer dispersion, and a combination of reactive solutions for obtaining the same.

b. Prior art 3a +4 +7 +7a-tetrahydroindene is
Zutadiene and cyclopentadiene Diels-Ald
It is obtained as a by-product in the erm reaction. This reaction of butadiene and cyclopentadiene has been industrialized as a method for producing ethylidenenorbornene by converting cyclopentadiene into a diene and gugudiene into an ene to obtain 2-vinylnorbornene, which is isomerized. Ethylidene norbornene is
It has been praised as the third component for EPDM rubber.

However, since the Dials-Alder reaction is a thermodynamic equilibrium reaction, butadiene becomes a diene and cyclopentadiene becomes an ene, and the following formula % formula % (THI) is produced as a by-product, albeit in a small amount. It can be obtained relatively cheaply as a by-product.

Such TRI has two cycloalkenes and has the potential to be used as a metathesis polymerization monomer. However, when attempting to polymerize this monomer itself using a metathesis catalyst, it was found that the activity was extremely low (and almost no monomerization occurred).

C1 Structure of the Invention Therefore, as a result of intensive research in order to obtain a good metathesis-polymerizable monomer derived from the Tl(I), TR
When I and cyclopentadiene were further reacted by Diels-Fulder reaction to form a 1-to-1 adduct (TPA), it was found that this monomer could form a good monomerization, and the present invention was achieved.

According to gas chromatography and mass spectrogram measurements, the 1:1 adduct has two types of adducts having the following U structure, that is, the cyclopentene side is ene, and
It is thought that there are two types: one with Dials-Alder addition (It) and one with Dials-Ald@r addition with ene on the cyclohexene side (III), and since there is no big difference in addition reactivity between both sides, selectively only some of them are added. (II) and (III) are always produced in a ratio close to that of the two, and since they are isomers with very similar structures, it is difficult to separate them by distillation, and it is difficult to separate them by distillation. obtained as.

This is thought to be due to the fact that all of these have a partial structure trapping norbornene ring with high metathesis polymerizability, but they are easily metathesized and have a rigid ring structure.
Therefore, the present invention was achieved by discovering that a Kurihashi 1 coalescence type product having a high secondary dislocation point can be obtained.

It is advantageous to obtain the polymer molded product at once rather than polymerizing in bulk and pouring the liquid monomer directly into the mud, and performing the polymerization and molding in one step. I discovered something.

In this case, since the metathesis polymerization reaction occurs at a very high speed, after the catalyst system components are mixed and before being injected into the wholesaler,
Polymerization occurs and injection into the mold is often difficult, but the main Pf! of the metathesis catalyst system! It has been found that it is possible to prepare the i-media component and the activator component as monomer solutions separately, mix these two components at high speed using collision mixing or a static mixer during injection, and then pour them into the mold at ℃. Ta. Furthermore, by replacing a part of TPA with other metathesis agents, not only can polymers be obtained without any problems, but depending on the selection of the cooperating agents, the characteristics of the polymer molded product can be improved. It has also been found that other characteristics can also be added.

That is, the present invention was arrived at through research and research, and includes the following inventions (1) to (3).

(1) Substantially from a mixture of a 1:1 adduct of 3a,4,7m-tetrahydroindene and cyclopentadiene resulting from the Diels-Alder reaction or a mixture of the Vil & adduct and at least one other monomer capable of monomerization A crosslinked monomer molded product obtained by polymerizing target raw material monomers in the presence of a metathesis polymerization catalyst system.

121 Substantially from a one-to-one adduct of 3m,4,7.7a-tetrahydroindene and cyclopentadiene resulting from the Diels-Alder reaction or a mixture of the adduct and at least one other metathesis-transforming mo/mer. A method for producing a crosslinked 1-combination molded product, which comprises bulk polymerizing target raw material monomers in the presence of a metathesis 1-polymerization medium, and performing molding at the same time as the 1-combination.

(31m, a reactive solution (solution KA) of a cyclic olefin, which is a catalyst for a metasense polymerization catalyst system; b, a reactive solution (bath solution B) of a cyclic olefin containing an activator for a metasense polymerization catalyst system; In a combination of reactive solutions that react by mixing,
The cyclic olefin in bath solution A and solution B has a combined composition of 3m, 4.7+7a-tetrahydroindene and cyclopentadiene in a 1:1 adduct formed by the Diels-Fulder reaction trap or tUt addition. 1. A reactive solution combination characterized in that the starting monomer consists essentially of a mixture of a monomer and at least one other meta-7cis polymerizable monomer.

The monomer used in the present invention is 3a+4.7.
The one-to-one adduct (TPA) produced by the Diels-Alder reaction of 7a-tetrahydroindene (TRI) and cyclopentadiene is a mixture of two compounds having the structures of formulas (II) and (111). This is estimated from gas chromatography and mass spectrogram.

In addition to this TPA, when performing the Diels-Alder reaction between THI and cyclopentadiene, a trimer of cyclopentadiene is produced, but this trimer has a boiling point of TP.
It is very close to A and is extremely difficult to separate by distillation.

However, this trimer also has metathesis and summerization properties, so even if some of this trimer is mixed in, there is no problem in the polymerization of the present invention (
Moreover, the properties of the obtained polymer are not impaired.

Therefore, if a constant amount of mixture can be maintained depending on the generation conditions,
It can be subjected to polymerization as it is or as a raw material monomer.

The raw material monomer such as TPA of the present invention preferably contains as little polar compounds as possible, such as alcohols, carboxylic acids, and carbonyl compounds, which inhibit metathesis polymerization.

As the raw material monomer of the present invention, TPA itself can be used, but other metathesis 1 can be used in any proportion to TPA.
At least -21 (copolymerizable monomer) of the polymerizable monomer can be mixed and used. As such copolymerizable monomers, various monomers can be used as long as they have optical metathesis polymerizability at ℃.

As the copolymerizable monomer, from the viewpoint of metathesis polymerizability, cycloalkenes other than cyclohexene, cyclobutene, cyclopentene, cycloheptene, cyclooctene, or substituted salt conductors thereof can be used. A compound having at least a norbornene skeleton in its molecule is preferable.

A preferred example of such a common X-table knob is TPA.
Here are some examples of how monomers that are easily mixed in during the production process can be used as they are without being forcibly removed to make monomer synthesis more advantageous, and examples where new properties can be imparted to the polymers of the present invention to make them more distinctive. I can do it.

An example of the former is as mentioned above. Furthermore, 5-ethylidene bisic a (2,2+1) pepto2
-2-6-3-tylidene-1,415,8-:)methano-L4
+5+7+8.8a-Hexahydronaphthalene and the like can also be mentioned as possible contaminants, but of course, separately synthesized ones may be added in the necessary amount.

Examples of the latter include those containing two or more metathesis-polymerizable groups in one molecule and having the effect of increasing the degree of crosslinking of the resulting polymer (A), and those containing organic Lewis space polar groups that can be heated at °C. Things that improve chemical resistance and heat resistance by adjusting the rate of metathesis point formation or introducing polar groups into the molecular chain5C
B), those containing halogen atoms and effective in flame retardation (C), etc. are preferred.

Specific examples of the above (A) include dicyclopentadiene,
1*4+5t8-dimeth/1 +4 s4&y5
t8.8a-hexahydro-naphthalene, tricyclo-(8v2slsO3) lysocar 5,11-diene,
Examples include 1,3-phenylenebis(5-norbornenyl).

Examples of the Lewis space in CB) include cyano A, a carboxylic acid ester group, and an ether group.

Examples include tertiary amide groups such as N,N-disubstituted amide groups, N-substituted imido groups, and pyridyl groups. (B)
Typical examples of compounds belonging to the group include 5-cyanonorbornene, 5-meth)=? Dicarbonylnorbornene, 5-7
') Kisiturubo I Renen.

Examples include 5-7cetia xynorbornene, 5-methyl-butoxycarbonylnorbornene, N-dutylnadenic acid imide, 5-norbornenylcarbonyl dispersion-N,N-dimethylamide, 5-(4-pyridyl)norbornene, etc. I can do it.

As an example of (C) above, °C is 5-(4-bromophenyl)
It is possible to give norbornene etc.

Furthermore, as bifunctional hydrocarbon norbornene derivatives for metathesis polymerization, 5-butylnorbornene, 5-impropenylnorbornene, 5-phenylnorbornene, 5-ethylidenenorbornene, cyclopentadiene-methylcyclopentadiene, etc. dimer, 1*4
Examples include t5+8-dimethano-1v4+41,5+8.8&-octahydronaphthalene.

Among the copolymerizable monomers mentioned above, especially dicyclopentadiene, 5-ethylidenebicyclo(21211) to 7'-
2-En. 5-cyanonorbornene, 5-furufkidicarbonylnorbornene.

5-Methyl-alkoxycarbonylnorbornene, N-
Preferred are alkyl nadic acid oxides and the like.

Such a copolymerizable monomer contains 0 to 0 in the raw material monomers containing TPA.
A range of 95 mole % is used.

Metathesized polymers from TPA have high T as described below.
Therefore, TPA is extremely effective as a copolymer component for improving the Tg of other metathesis polymers.In that case, it becomes effective from a usage rate of about 5 mol%. For this reason, a wide range of TPs as mentioned above
The usage ratio of the copolymer component to A becomes effective.

Therefore, the copolymerization ratio of TPA in order to improve the properties of the TPA polymer is preferably within the range of 5 to 50 mol%; conversely, when TPA is used as a Tg improver, In this case, it is preferably 50 to 95 mol%, particularly 40 to 10 mol%.

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

For such bulk polymerization, there is a method of first adding an active agent component to a single raw material, then adding a main catalyst component, and making a sample before polymerization starts and gelation occurs to obtain a crosslinked product. It is also possible to add the main catalyst component and other active agent components to the raw material monomer at the same time to obtain a crosslinked product in the same way. However, the Metacera 31 polymerization reaction is generally an exothermic reaction, and once the polymerization starts, the reaction system is further heated and the reaction speeds up, completing the reaction at a very high speed. However, it is often difficult to store the gelling agent using the methods described above.

Therefore, as mentioned above, two solutions are prepared in advance: a solution containing the main catalyst component of the metathesis catalyst system (solution A) and a solution containing other active agent components (solution B) together with the raw material monomer. Appropriate methods include the collision mixing (CRIM) method, rapid mixing using a static mixer, etc., direct injection into a mold for trial production, and then polymerization hardening and production indoors. In this case, the composition of the raw material monomers does not necessarily need to be the same in both solutions, and can be arbitrarily changed as long as the overall composition of the monomers falls within the above-mentioned range.

Regarding the production of molded products by such metathesis polymerization and filtration and two-liquid mixing method, JP-A-58-129.0 describes the case where dicyclopentadiene is used as a monomer.
It is disclosed in Publication No. 13.

The catalyst component in the metathesis polymerization catalyst system in the above-mentioned molding method is tungsten.

Salts such as halides such as rhenium and tantalum 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. Organic ammonium tungstates may also be used.

Such tungsten compounds are not preferred because they are known to immediately start cationic polymerization when added directly to the raw material monomers. 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.

Further, in order to prevent the undesirable reaction 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. Examples of such additives include acetylacetone, acetoacetic acid furkyl esters, tetrahydrofuran, and benzonitrile. If a co-merging monomer having a Lewis space group is used, it can also serve this role. By doing so, the catalyst,
In particular, a reactive solution containing a tungsten compound (corresponding to solution A) will have sufficient stability when used in practical use.

On the other hand, the active ingredient in the metathesis synthesis catalyst system is an organometallic compound mainly containing a fullylated metal of Groups 1 to 2 of the periodic system, particularly tetraalkyltin and alkylaluminum compounds.

Preferred are alkyl aluminum pallite compounds, specifically diethylaluminicum chloride.

Examples include ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin.

The other solution (corresponding to solution B) is formed by dissolving the organometallic compound 71 as the activator component in the raw material monomer.

In the present invention, a crosslinked pentapolymer molded article can basically be obtained by mixing the solutions A and B, but the polymerization reaction will start very quickly if the above composition remains as it is. However, hardening may occur before it has sufficiently flowed into the casting pot, which often poses a problem (for this reason, it is preferable to use an activity regulator).

As such a regulator, Lewis bases are generally used, and among them, ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. Such a part is generally used by adding it to the side of the solution of the activator component of the organometallic compound. can serve as a regulator.

The amount of the metathesis synthesis catalyst system used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the upper Me raw material monomer is about 1000:1 to about 15000:1, preferably 2000:1 on a molar basis.
In addition, when an alkyl aluminum is used as the activator component, the ratio of the aluminized product to the raw material monomer is about 100 to 1 on a molar basis.
A ratio of about 2000:1, 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 the fA clause as appropriate depending on the amount of the catalyst system to be used through trial.

In practical use, various additives may be added to the molded article of the present invention in order to improve or maintain its properties. Such additives include fillers, pigments, antioxidants, light stabilizers, polymer modifiers, and the like.

It is impossible to add such additives after the crosslinked polymer of the present invention has been molded, so if they are added, it is necessary to add them to the above-mentioned raw material solution in advance and keep it at ℃.

The easiest method is to use Shuki Solution A and Solution B.
It is possible to add it in advance to either or both of the following methods: In addition, it must not inhibit polymerization.

If the reactions are unavoidable but they coexist and do not substantially inhibit polymerization, mix with the monomer to prepare a third liquid, and mix and use immediately before the first reaction. You can also do that. In the case of a solid filler, the g! It is also possible to fill a mold with a shape that can sufficiently fill the gap.

Additive reinforcements or fillers are effective in increasing flexural modulus. Examples of such materials include glass fiber, mica, carbon blank, and wollastonite.

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 pentapolyte molded product of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. As a specific example of these antioxidants, the temperature is 2.6°C.
- t-butyl-P-cresol, N,N'-diphenyl-p-7 ethylenediamine, tetrakis[methylene (3,5-di-t-butyl-4-human-xycinnamate))methane, methylene-4 , 4'-bis(3,5-di-t-butylphenol), and the like.

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 increases the resistance of molded products to 9
#Effective in increasing the impact resistance and adjusting the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-inprene-styrene triblock rubber,
Polybutadiene, polyimprene.

A wide variety of elastomers can be mentioned, including butyl rubber and ethylene propylene-genter polymers.

The polymer molded article of the present invention is preferably produced by simultaneously carrying out polymerization and formation, as described above. According to the so-called R I M method! It is preferable to build 8i. In RIM molding (as mentioned above, a single-substance solution (that is, solution A and bath liquid B) in which the catalyst component and the activator component are dissolved separately is rapidly formed in the mixing head of the RIM machine. A common method is to obtain a C molded product by mixing, injecting into a mold, polymerizing and molding.

Since the injection pressure into the i# mold (mold) is relatively low, it is possible to use an inexpensive mold.

Six-man pressure on the mold can be used at relatively low pressures, thus allowing the use of inexpensive molds. Also, 7! ! When the circular polymerization reaction starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike the case of polyurethane-RIM, it is easy to release from the mold and often does not require special demolding.

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

From the viewpoint of the reaction characteristics of the Metacera 31 polymer, the 1 polymer of the present invention is considered to be a copolymer with the following structure.

Since it contains many rigid annular structures, it provides a composite product with high Tg and excellent performance.

Therefore, this is an extremely industrially advantageous combination of a crosslinked polymer composition, its production method, and a reactive solution.

The obtained molded product can be used in a wide range of applications, mainly large molded products, such as parts for various transportation equipment including automobiles, air conditioning, and /S housing for 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.

Example 1-10. Comparative Example Commercially available 31114.7.711-tetrahydroindene (T) II) and cyclopentadiene were subjected to a Dials-Alder reaction in an autoclave, followed by distillation under a nitrogen stream, and purity was determined by gas chromatography.
The ratio of F, MBHI, and cyclopentadiene triad is 1:
A 2:2 mixture (TPA mix '4J) was obtained. On the other hand, commercially available dicyclopentadiene (DCP) was similarly distilled to obtain a product having a freezing point of 33.4°C.

[v of catalyst component solution! 4g] 20p of tungsten hexachloride in dry toluene 70ILtK
ffl was added under atmospheric pressure, and then nonylphenol 2
A bath solution consisting of 1 g and toluene 16517 was added.
．． A 5 M tungsten-containing phase medium solution was prepared, and the solution was heated with nitrogen gas at 1 (-m/<-diC) to remove hydrogen chloride gas produced by the reaction of tungsten hexachloride and nonylphenol. This was used as a catalyst solution for synthesis.

Such a solution [10d, acetylacetone 1.0d mixed monomer soomt'tm, tungsten gold wave 0.001
M solution A was manufactured by EA.

[Preparation of active agent component solution]

Diethyl aluminum chloride 0.18 &.

Isopropyl ether 0.375 Lt mixed single basin 5Q
QR1 is mixed and the aluminum content is 0.003°C.
The compositions of the monomers used in the solution M, A, and B were as follows.

The above solution was converted into catalyst component solution (solution A) x Oa4
Activation active ingredient solution B) 10JIj to internal temperature 25
The mixture was kept at ℃ and then taken out into a syringe which was replaced with 9 ml. An extremely durable three-dimensional polymer molded product in the form of a plate was obtained by extruding the ring at a constant speed, injecting a liquid, mixing it in a nozzle, and applying it to an ultra-compact RIM machine that can be poured into a mold.

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 10, the values are roughly the same, and all of them show high polymerizability.

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

When measuring the softening point using TMA, the addition of TPA dramatically improves the softening point. Furthermore, when the softening points of the samples heated to 280° C. under N were measured again, they were all quite high, indicating the possibility of improving the softening point through post-treatment.

The swelling rate tends to increase somewhat as the copolymerization ratio of DCP increases, probably because the degree of crosslinking of the TPA homopolymer is somewhat lower than that of DCP.

Claims (3)

[Claims] (1) Substantially more than a one-to-one adduct of 3a,4,7,7a-tetrahydroindene and cyclopentadiene resulting from the Diels-Alder reaction, or a mixture of the adduct and at least one other metathesis polymerizable monomer. A crosslinked polymer molded product obtained by polymerizing raw material monomers in the presence of a metathesis polymerization catalyst system. (2) Substantially more than a one-to-one adduct of 3a,4,7,7a-tetrahydroindene and cyclopentadiene resulting from the Diels-Alder reaction or a mixture of the adduct and at least one other metathesis-polymerizable monomer. 1. A method for producing a crosslinked polymer molded article, which comprises bulk polymerizing raw material monomers in the presence of a metathesis polymerization catalyst system and molding simultaneously with the polymerization. (3) Consists of at least a, a reactive solution of a cyclic olefin containing a metasense polymerization catalyst system catalyst (solution A), b, a reactive solution of a cyclic olefin containing an activator of a metathesis polymerization catalyst system (solution B), and both In the combination of reactive solutions that react by mixing, the cyclic olefins in solution A and solution B have a combined composition of 3a, 4, 7,
The raw material monomer consists essentially of a one-to-one adduct of 7a-tetrahydroindene and cyclopentadiene resulting from a Diels-Alder reaction, or a mixture of the adduct and at least one other metathesis-polymerizable monomer. Characteristic combination of reactive solutions.