JPH05178969A - Molded thermoset resin article - Google Patents

Abstract

PURPOSE:To provide a molded thermoset norbornene resin article having a high heat distortion temp., a high bending modulus, and a good impact resistance. CONSTITUTION:A norbornene monomer is polymerized in bulk in the presence of both a metathesis catalyst and an arom. vinyl compd. isobutylene block copolymer, thus giving a molded thermoset resin article.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin molded article obtained by bulk polymerization of a norbornene-based monomer in the presence of a metathesis catalyst system. More specifically, the present invention relates to a metathesis catalyst system in the presence of a specific elastomer. The present invention relates to a thermosetting resin molded product obtained by bulk polymerization of a norbornene-based monomer. The thermosetting resin molding has a high heat distortion temperature, an improved flexural modulus and good impact resistance. This thermosetting resin is used in a wide range of applications including large molded products such as automobiles, agricultural equipment, members of construction equipment, and housings of electric and electronic equipment.

[0002]

2. Description of the Related Art Tricyclic or tetracyclic norbornene-based monomers such as dicyclopentadiene (DCP), methyltetracyclododecene (MTD) and ethylidenetetracyclododecene are used alone or appropriately by reaction injection molding (RIM). It is well known that a norbornene-based polymer can be obtained by performing bulk polymerization in combination in the presence of a metathesis catalyst system (consisting of a metathesis catalyst and a cocatalyst) in a mold (JP-A-58-129013, JP-A-58-129013). Sho 59-51
No. 911, JP-A-61-179214, JP-A-61-
293208).

According to such a method, it is possible to manufacture a large-sized molded product having a high heat distortion temperature, elastic modulus and impact resistance with an inexpensive mold and molding equipment. However, in recent years in the field of large molded articles, higher heat distortion temperature, elastic modulus and impact resistance are required, and improvement of norbornene-based polymer is desired. To increase the impact strength of a norbornene-based polymer obtained by bulk-polymerizing a norbornene-based monomer, a hydrocarbon-based rubber that is soluble in the monomer is generally used. For example, styrene-butadiene rubber (SBR), butadiene-styrene block copolymer (SBS), butadiene-isoprene block copolymer (SIS), poly-cis-1,4-
Butadiene (BR), poly-cis-1,4-isoprene (IR), hydrogenated product of styrene-ethylene-butadiene block copolymer (SEBS), natural rubber, polyisobutylene rubber, ethylene-propylene rubber, ethylene-
Propylene-diene-terpolymer rubber (EPDM or EPT), butyl rubber (IIR) and the like are known.

However, generally, the impact resistance represented by the Izod impact value of plastics and the heat resistance represented by the heat distortion temperature are contradictory properties, and have a trade-off relationship. In the case of a norbornene-based polymer, if a large amount of elastomer is added to improve impact resistance, heat resistance and elastic modulus decrease. In this way, it has been conventionally difficult to satisfy both requirements to improve impact resistance while increasing heat resistance and elastic modulus.

[0005]

The inventors of the present invention have diligently studied an elastomer additive for a norbornene-based polymer in order to solve the above-mentioned incompatible problems. As a result, a specific elastomer is suitable for this purpose. The present invention has been completed and the present invention has been completed.

[0006]

Thus, according to the present invention, there is provided a thermosetting resin molded article obtained by bulk polymerization of a norbornene-based monomer in the presence of a metathesis catalyst system, which comprises an aromatic vinyl compound and isobutylene. Provided is a thermosetting resin molded article, which is obtained by bulk-polymerizing a norbornene-based monomer in the presence of a copolymer consisting of

The present invention will be described in detail below. (Norbornene-based Monomer) In the present invention, a norbornene-based monomer having a tricyclic structure or more is used in order to obtain a polymer having good heat distortion temperature, impact resistance and flexural modulus.

Examples of the tricyclic norbornene monomer include dicyclopentadiene (DCP), dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer and 6-ethylidene-1,4,5,5.
8-dimethano-1,4,4a, 5,7,8,8a-heptahydronaphthalene, 1,4-methano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene and the like can be mentioned.

Tetracyclic norbornene monomers include tetracyclododecene and methyltetracyclododecene (M
TD), ethyltetracyclododecene, dimethyltetracyclododecene, ethylidenetetracyclododecene, vinyltetracyclododecene, phenyltetracyclododecene and the like.

Examples of pentacyclic norbornene monomers include tricyclopentadiene (TCP). TCPs are dicyclopentadiene (DCP) s in an inert gas atmosphere at 120 to 250 ° C. for 0.5 to 2
It can be obtained by heat treatment for 0 hours. DC
By heat treatment of Ps, a monomer mixture containing TCPs and unreacted dicyclopentadiene is obtained.

In the present invention, TCPs may be isolated from the mixture according to a known method (for example, US Pat. No. 3,701,812), but the mixture may be used as it is without isolation. You can also In addition, a norbornene-based monomer having a polar group such as a halogen, an ester group, an ether group, a cyano group, an imide group, or a pyridyl group as a substituent can be used if desired. Among them, dicyclopentadiene (DCP) is favored from the viewpoint of easy availability. These norbornene-based monomers may be used alone or in combination of two or more.

A monomer capable of ring-opening polymerization can be used in combination with the above-mentioned tricyclic or higher norbornene-based monomer as long as the object of the present invention is not impaired. Specifically, ring-opening polymerizable 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2.
-Norbornene, 5-hexyl-2-norbornene, 5
-Bicyclic norbornene-based monomers such as ethylidene-2-norbornene, 5-phenylnorbornene, norbornadiene, or cyclobutene, cyclopentene,
Examples thereof include monocyclic cycloolefins such as cyclopentadiene, cyclooctene, and cyclododecene.

(Elastomer) The elastomer used in the present invention is a copolymer composed of an aromatic vinyl compound and isobutylene. The copolymer may be a random copolymer, but is preferably a block copolymer composed of a polymer block derived from an aromatic vinyl compound and a polymer block derived from isobutylene,
The block copolymer includes a diblock copolymer in which one polymer block derived from an aromatic vinyl compound and one polymer block derived from isobutylene are bonded; or an aromatic vinyl compound Induced 2
Triblock copolymer consisting of one terminal polymer block and one intermediate polymer block derived from isobutylene; and a polymer block derived from two or more isobutylenes and one or more aromatic vinyl compounds A multi-block copolymer having an intermediate polymer block in which more derived polymer blocks are alternately bonded and a terminal polymer block derived from two or more aromatic vinyl compounds is included. Also included are branched block copolymers, radial block copolymers having three or more terminal polymers, linear block copolymers, or mixtures of these polymers.

The method for producing the block copolymer of an aromatic vinyl compound and isobutylene is not particularly limited, but for example, according to the method described in Japanese Patent Application No. 80639 in 1990, a cationic polymerization in combination with Lewis acid and Lewis acid is carried out. In the presence of an initiator system composed of an organic compound that forms an active species (hereinafter referred to as an initiator compound), a third component such as amines is added, if necessary, and hexane, methylene chloride or the like is added. A method of polymerizing an aromatic vinyl compound and isobutylene in an inert solvent is adopted.

Here, the initiator compound is an organic compound having a functional group such as an alkoxy group, an acyloxy group or a halogen, for example, bis (2-methoxy-).
2-propyl) benzene, bis (2-acetoxy-2-)
Examples include propyl) benzene and bis (2-chloro-2-propyl) benzene. Examples of Lewis acid include titanium tetrachloride, and examples of amines include triethylamine.

Among the block copolymers, a method of obtaining a linear block copolymer is to use an initiator compound having one functional group such as halogen, an alkoxy group or an acyloxy group and a Lewis acid as an initiator system. After polymerizing the aromatic vinyl compound until the reaction is substantially completed,
It is possible to employ a method in which isobutylene is introduced into the system, and after the substantial polymerization reaction of isobutylene is completed, the aromatic vinyl compound is polymerized again. However, more preferably, an initiator compound having two of the above functional groups is used together with a Lewis acid to polymerize isobutylene until the reaction is substantially completed, and then an aromatic vinyl compound is introduced into the system. A method of continuing the polymerization reaction is adopted.
According to this preferable method, a block copolymer having a well-controlled molecular structure and molecular weight distribution can be obtained. As a method of obtaining a radial block copolymer, an initiator compound having three or more of the above functional groups is used together with a Lewis acid, and isobutylene is polymerized until the reaction is substantially completed. The polymerization reaction may be continued by introducing a group vinyl compound.

The aromatic vinyl compound used for producing the copolymer used in the present invention includes styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene and monochlorostyrene. , Styrene derivatives such as dichlorostyrene and methoxystyrene, and naphthalene derivatives such as α- or β-vinylnaphthalene.

The content of the aromatic vinyl compound in the copolymer elastomer used in the present invention is usually 5 to 50% by weight, preferably 10 to 45% by weight. If the content of the aromatic vinyl compound is excessively low, the solubility in norbornene-based monomers decreases, and the norbornene-based monomer compounding solution in which the elastomer is dissolved often becomes cloudy or a heterogeneous phase, and the norbornene obtained by bulk polymerization is obtained. The physical properties of the base polymer will also vary. On the other hand, if the amount is too large, the properties as an elastomer deteriorate, and the impact resistance of the norbornene-based polymer obtained by adding this decreases.

The number average molecular weight of the copolymer elastomer used in the present invention is preferably 30,000-5.
0,000, more preferably 50,000 to 400,
If it is less than 30,000, the properties as an elastomer deteriorate, and if it exceeds 500,000, the solubility in a norbornene-based monomer decreases,
In addition, the bulk polymerization operation becomes difficult because the viscosity upon dissolution increases.

The amount of the copolymer elastomer used is usually 1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the monomer mixture. If the amount of the elastomer used is too small, the effect of improving the impact strength is low, and if it is too large, the flexural modulus decreases. The copolymer elastomer is used alone or in combination of two or more. The aforementioned hydrocarbon-based elastomer such as SBR can be used in combination with the elastomer according to the present invention as long as the effects of the present invention are not impaired.

(Metathesis Catalyst System) In producing the thermosetting resin molded article of the present invention, the catalyst used for bulk ring-opening polymerization of norbornene-based monomers is a metathesis catalyst known as a catalyst for bulk ring-opening polymerization of norbornene-based monomers. Any system may be used (for example, JP-A-58-1277).
No. 28, No. 58-129013, No. 59-51911.
No. 60-79035, No. 60-186511,
No. 61-126115), and there is no particular limitation. A metathesis catalyst system usually consists of a metathesis catalyst and an activator (cocatalyst).

Specific examples of the metathesis catalyst include halides such as tungsten, molybdenum, tantalum and ruthenium, oxyhalides, oxides and organic ammonium salts. Among the metathesis catalysts,
It is preferable to use a catalyst that is soluble in the norbornene-based monomer used in the reaction, and from that standpoint, organic ammonium salts are preferred. When the catalyst is a halide, it can be solubilized by treating it with an alcohol compound or a phenol compound in advance. Also,
If necessary, a Lewis base such as benzonitrile or tetrahydrofuran or a chelating agent such as acetylacetone or alkyl acetoacetate can be used in combination, whereby premature polymerization can be prevented.

Specific examples of the activator include alkylaluminum, alkylaluminum halide, alkoxyalkylaluminum halide, aryloxyalkylaluminum halide and organic tin compound. Among the activators, alkoxyalkylaluminum halides and aryloxyalkylaluminum halides have a suitable pot life at room temperature even when mixed with a catalyst component, and are advantageous in operation (for example, JP-A-59-51911). ). In the case of alkylaluminum halide, there is a problem that polymerization starts immediately when a catalyst is mixed, but in that case, an activator and a regulator such as ethers, esters, ketones, nitriles, alcohols, etc. are used together. By doing so, the initiation of polymerization can be delayed (for example, JP-A-58-129013).
No. 61-120814).

In addition to the catalyst and activator, a halogenated hydrocarbon such as chloroform, carbon tetrachloride, hexachlorocyclopentadiene, etc. may be used in combination (for example, JP-A-60-79035). Further, halides such as tin tetrachloride, silicon tetrachloride, magnesium chloride and germanium chloride may be used in combination (JP-A-63-1867).
No. 30).

The metathesis catalyst is usually used in an amount of about 0.01 to 50 mmol, preferably 0.1 to 10 mmol, relative to 1 mol of the norbornene-based monomer. The activator is generally used in the range of 0.1 to 200 (molar ratio), preferably 2 to 10 (molar ratio) with respect to the catalyst component. Both the metathesis catalyst and the activator are preferably used by dissolving them in the monomer, but they may be used by suspending or dissolving them in a small amount of solvent as long as the properties of the product are not substantially impaired.

(Bulk Polymerization) In the production of the thermosetting resin molded product of the present invention, the RIM method in which a norbornene-based monomer is subjected to bulk ring-opening polymerization in a mold in the presence of a copolymer elastomer with a metathesis catalyst is used. To be taken. It suffices if it is substantially bulk polymerization, and a small amount of an inert solvent may be present.

In a preferable method for producing a ring-opening polymer, a norbornene-based monomer mixture is divided into two liquids and placed in another container, a metathesis catalyst is added to one and a cocatalyst is added to the other, and two kinds of stable compounds are prepared. Prepare a reaction stock solution. These two types of reaction stock solutions are mixed and then poured into a mold having a predetermined shape, where ring-opening polymerization is carried out in a bulk form. The mold may be a simple mold.

In the present invention, a collision mixing device conventionally known as a RIM device can be used to mix two kinds of reaction stock solutions. In this case, the containers containing the two types of reaction stock solutions serve as separate flow sources. The two streams are mixed instantaneously with the mixing head of a RIM machine and then injected into a hot mold where they are immediately bulk polymerized to give a molding.

Further, after the two kinds of reaction stock solutions are mixed in the mixer, they may be injected or injected into the preheated mold several times (for example, JP-A-59-59).
51911, U.S. Pat. No. 4,426,502) or continuously. This method has the advantage that it can be downsized compared to an impingement mixing device and can be operated at low pressure, and it also has the advantage of increasing the injection speed when the amount of reinforcement such as glass fiber is large. By slowing down, it becomes possible to uniformly impregnate the reaction stock solution into the system.

The method for producing the thermosetting resin molded product of the present invention is not limited to the method using two kinds of reaction stock solutions. As will be readily appreciated by those skilled in the art, various modifications are possible, such as, for example, putting the monomer and the desired additive in the third container and using it as the third stream. The material of the mold used in the present invention is not particularly limited to metal,
Any of synthetic resin, wood, cement, etc. can be used, but from the economical point of view, a resin mold, a product having its surface plated, an electroforming mold, etc. are preferred.

The mold temperature is usually room temperature or higher, preferably 40 to 200 ° C, more preferably 50 to 120 ° C. The mold clamping pressure is usually within the range of 0.1 to 100 kg / cm ² . The reaction stock solution is usually stored and operated under an atmosphere of an inert gas such as nitrogen gas, but the molding die does not necessarily need to be sealed with an inert gas.

(Optional component) Antioxidant, filler, pigment,
By adding various additives such as a colorant, a foaming agent, a flame retardant, a sliding agent, a dicyclopentadiene-based thermopolymerized resin and a hydrogenated product thereof, the properties of the obtained polymer can be modified.

As the antioxidant, there are various phenol-based, phosphorus-based, amine-based antioxidants for plastics and rubbers. Fillers include inorganic fillers such as milled glass, carbon black, talc, calcium carbonate and mica. The additive is usually mixed in advance with one or both of the reaction solutions.

[0034]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Further, parts and% in these examples are based on weight unless otherwise specified.

Reference Example Production Example of Block Copolymer and Its Physical Properties Methylene chloride 500 was placed in a reactor under a dry nitrogen atmosphere.
Parts, n-hexane 500 parts, 1,4-bis (2-chloro-2-propyl) benzene 0.76 parts, triethylamine 0.83 parts and the amount of isobutylene shown in the experiment number of Table 1 were added respectively to -65. Cooled to ° C. 16 parts of a 0.3 molar solution of titanium tetrachloride in methylene chloride / n-hexane (volume ratio 1/1) that had been cooled to −65 ° C. in advance was added to initiate the polymerization reaction. After 4 hours, the amounts of styrene shown in the experiment numbers in Table 1 were added, and the polymerization reaction was continued for another 2 hours. Then, 200 parts of methanol was added to the polymer solution to stop the polymerization reaction. Next, toluene was added to dissolve the polymer, and then 2% hydrochloric acid aqueous solution, water, 2
% Sodium hydroxide aqueous solution and water were washed in this order.
A large amount of methanol was added to the solution after washing to precipitate the polymer, and the solvent was removed to obtain three kinds of styrene-isobutylene-styrene block copolymers (SIBS). The yield of each polymer was substantially 100%.

The bound styrene content of the block copolymer obtained, determined by NMR, and the average molecular weight and the heterogeneity index of the molecular weight distribution measured by gel permeation chromatography (ratio of the weight average molecular weight to the number average molecular weight). ) Is shown in Table 1.

[Table 1]

The weight average molecular weight and molecular weight distribution of the obtained block copolymer were determined from the molecular weight distribution curve measured by high performance liquid chromatography (HLC-802A, manufactured by Toso Co., Ltd.). It was calculated based on a calibration curve previously obtained from the analysis results of known standard polystyrene. Column G filled with polystyrene gel for measurement
-4000H and G-5000H were used in combination, and the measurement was carried out under the conditions of a column temperature of 40 ° C, a carrier (tetrahydrofuran) flow rate of 1.3 (ml / min), and a sample concentration of 0.6 (g / 1).

Examples 1-3 and Comparative Examples 4-8 2,6-di-t-butyl-4-hydroxytoluene (B
HT) containing 100 ppm of dicyclopentadiene (DCP) having a purity of 99.5% and tricyclopentadiene (TCP) having a purity of 96.1% at a ratio of 90:10. 4 parts of the elastomer of 2 were dissolved. The mixture was divided into two equal parts, one containing 41 mmol / l of diethyl aluminum chloride (DEAC) and 50 mmol / l of n-propyl alcohol.
1 and silicon tetrachloride were added so as to have a concentration of 20 mmol / l and mixed well to prepare a solution A.

On the other hand, 4 parts of Irganox 1010 (manufactured by Ciba Geigy), which is a phenolic antioxidant, and tri (dodecyl) ammonium molybdate are added so as to have a concentration of 12 mmol / l and mixed well. This is liquid B. Both A and B reaction solutions were mixed at a ratio of 1: 1 using a gear pump and a power mixer, and 300 mm x 300 mm x 3 mm
The mixture was poured into a mold heated to 60 ° C. having a space volume of 100 ° C. at almost normal pressure. The injection time was about 30 seconds. After the injection was completed, the reaction was performed for 90 seconds. Then, the molded product (norbornene-based monomer) was taken out from the mold, and the physical properties were measured. The results are shown in Table 2.

[Table 2]

Note: * 1 Elastomer SIBS: Styrene-isobutylene-styrene block copolymer IIR: Butyl rubber SBS: Butadiene-styrene block copolymer SEBS: Hydrogenated butadiene-styrene block copolymer * 2 Load 18.5 kg / Measured at cm ² * 3 Measured at 23 ° C. As is clear from Table 2, the thermosetting resin molded product of the present invention obtained by using SIBS is compared with those obtained by using other commercially available elastomers. , High heat distortion temperature, impact resistance, flexural modulus.

[0041]

INDUSTRIAL APPLICABILITY The thermosetting resin molded product of the present invention obtained by adding the block copolymer composed of an aromatic vinyl compound and isobutylene has a high heat distortion temperature and a high bending elastic modulus and, at the same time, has an impact resistance It is good, and its moldability is also good. INDUSTRIAL APPLICABILITY The thermosetting resin molded product of the present invention can be used in a wide range of applications including large molded products such as automobiles, agricultural equipment, members of construction equipment, and housings of electric and electronic equipment.

Claims (1)

[Claims] 1. A thermosetting resin molding obtained by bulk polymerization of a norbornene monomer in the presence of a metathesis catalyst system, wherein the norbornene monomer is present in the coexistence of a copolymer of an aromatic vinyl compound and isobutylene. A thermosetting resin molded product, which is obtained by bulk polymerization of.