JPH0819220B2 - Method for producing norbornene-based polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a norbornene-based polymer by bulk-polymerizing a norbornene-based monomer in the presence of a metathesis catalyst system, and more specifically, to impair polymerization activity. The present invention relates to a method for producing a norbornene-based polymer capable of controlling the pot life of a reaction stock solution arbitrarily.

2. Description of the Related Art Conventionally, a method of bulk-polymerizing a norbornene-based monomer such as dicyclopentadiene or methyltetracyclododecene is known.

For example, in JP-A-58-129013, a dicyclopentadiene (DCP) homopolymer using a metathesis catalyst system (metathesis catalyst system) by a reaction injection molding method (hereinafter sometimes referred to as "RIM method"). Is disclosed, in which the homopolymer is a reaction injection mixture of two kinds of monomer mixture solution (reactant stream) that separately contains each part of a metathesis catalyst system consisting of two parts, a catalyst and an activator. It is manufactured by mixing with a mixing head of a molding machine (RIM machine) and then pouring it into a molding die. In a preferred embodiment, one of these two parts contains a tungsten-based metathesis catalyst and a monomer (DCP), the other part contains a metathesis catalyst activator and a monomer (DCP) such as an alkylaluminum halide, and an activity modifier. As an ether, ester or ketone.

By the way, in the above catalyst system, since the polymerization reaction proceeds immediately when the two reactant streams are mixed (the pot life of the mixed reaction stock solution is several minutes or less at room temperature), the mixing is performed immediately before filling the mold. There is no choice but to adopt the collision mixing method. This impingement mixing method requires a large amount of force in the mixing stage, and also needs a large pressure to inject the reaction stock solution into the mold, so that there is a drawback that the cost of the RIM machine for that purpose becomes high.

On the other hand, JP-A-59-51911 and JP-A-61-12081.
In JP-A-45-45, the use of alcohol as an activity modifier for prolonging the pot life is proposed in bulk polymerization of norbornene-based monomers by the RIM method. According to this method, the pot life can be considerably prolonged as compared with the method disclosed in Japanese Patent Laid-Open No. 58-129013. Therefore, it does not require a large force to mix the reactant streams, the injection into the mold can be done at low pressure, and it is possible to fill the reaction stock solution into the mold in several batches. It has an advantage that cost reduction and size reduction can be achieved. It is also possible to premix the two reactant streams. However, in the case of the conventional alcohol-based activity regulator, there is a problem that the pot life extension effect is still insufficient.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Therefore, the inventors of the present invention have conducted diligent research to find an activity regulator having a large pot life prolonging effect without impairing the polymerization activity. In the method for producing a norbornene-based polymer in which bulk polymerization is performed, by using a monoether and / or a monoester of a glycol compound selected from alkylene glycol or polyalkylene glycol as an activity modifier, the pot life of the reaction stock solution at room temperature is conventionally reduced. The present invention was completed based on the findings that it was extended more than the method and that it polymerized rapidly at high temperatures.

Means for Solving the Problems Thus, according to the present invention, a norbornene-based monomer essentially consists of a tungsten-based or molybdenum-based catalyst (A), an organoaluminum-based activator (B) and an activity modifier (C). In the method of producing a norbornene-based polymer by bulk polymerization in the presence of a metathesis catalyst, a monoether and / or monoester of at least one glycol compound selected from alkylene glycol and polyalkylene glycol is used as the activity modifier (C). A method for producing a norbornene-based polymer is provided.

By adopting the above configuration, the pot life of the reaction stock solution can be greatly extended, and the polymerization reaction in the mold can proceed in a short time as in the conventional case because the polymerization activity of the catalyst is not impaired. The physical properties of the obtained polymer are also good. Here, the pot life is the time during which the polymerization of the reaction stock solution (reaction mixture) at room temperature conditions remains in a substantially stopped state, and after mixing the components for forming the reaction stock solution,
It means the time until the initiation of polymerization of the monomer under room temperature conditions.

 Hereinafter, the components of the present invention will be described in detail.

(Norbornene-based Monomer) The norbornene-based monomer that can be bulk-polymerized according to the production method of the present invention is a substituted and unsubstituted polycyclic norbornene having two or more rings, and specific monomers include, for example, 2-norbornene and 5-methyl-2-
Norbornene, 5,6-dimethyl-2-norbornene, 5
-Bicyclic norbornenes such as ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, dicyclopentadiene, dihydrodiene Tricyclic norbornene such as cyclopentadiene,
Tetracyclododecene, methyltetracyclododecene,
Examples thereof include tetracyclic norbornene such as ethyltetracyclododecene and dimethyltetracyclododecene, and polycyclic norbornene such as tricyclopentadiene and tetracyclopentadiene. Among these norbornene-based monomers, tricyclic or pentacyclic norbornene is preferable.

It should be noted that a mono- or dicycloolefin such as cyclobutene, cyclopentene, cyclooctene, or cyclododecene capable of ring-opening polymerization with one or more of the above norbornene-based monomers can be used in combination within a range not impairing the object of the present invention.

(Metathesis Catalyst System) The catalyst used in the present invention is a metathesis catalyst system consisting essentially of a tungsten-based or molybdenum-based catalyst component (A), an organoaluminum-based activator (B) and an activity modifier (C). .

Metathesis Catalyst As the metathesis catalyst component (A), tungsten or molybdenum halide, oxyhalide,
Examples thereof include oxides and organic ammonium salts. Suitable examples are tungsten hexachloride, tungsten oxytetrachloride, tungsten oxide, tridodecyl ammonium tungstate, methyl tricapryl ammonium tungstate, tri (tridecyl) ammonium tungstate. , Tungsten compounds such as trioctyl ammonium tungstate: Molybdenum compounds such as molybdenum pentachloride, molybdenum oxytrichloride, tridodecyl ammonium molybdate, methyl tricapryl ammonium molybdate, tri (tridecyl) ammonium molybdate, trioctyl ammonium molybdate and so on. Among them, it is preferable to use a catalyst that is soluble in the norbornene-based monomer used in the reaction, and from that viewpoint, an organic ammonium salt is awarded. When the catalyst is a halide, the catalyst can be solubilized by pretreatment with an alcohol compound or a phenol compound. 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 (for example, JP-A-58). -129013).

Organoaluminum Activator On the other hand, an alkylaluminum halide is used as the organoaluminum activator (B) that acts as a cocatalyst.

Suitable examples include ethyl aluminum dichloride,
Diethyl aluminum chloride, ethyl aluminum sesquichloride, diethyl aluminum iodide, ethyl aluminum diiodide, dipropyl aluminum chloride, propyl aluminum diiodide, diisobutyl aluminum chloride, dihexyl aluminum chloride, dioctyl aluminum chloride, ethyl aluminum dibromide, methyl aluminum Examples include sesquichloride and methylaluminum sesquibromide.

Activity modifier As the activity modifier (C), an alkylene glycol monoether or monoester, and a polyalkylene glycol monoether or monoester, or a mixture thereof is used.

Specific examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,
Examples thereof include 6-hexanediol, 2,5-hexanediol, 2-chloro-1,3-propanediol, and among others, those having an alkylene group having 2 to 6 carbon atoms are preferable.
Specific examples of the polyalkylene glycol include those having a low degree of polymerization such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, dibutylene glycol, tributylene glycol, and the like. Polyethylene glycol and polypropylene glycol with a high degree of polymerization of up to about 2,000 can be used.

As a substituent introduced into these glycols to form an ether bond, an alkyl group having about 1 to 10 carbon atoms is preferable. As the substituent forming an ester bond, an acyloxy group having about 2 to 10 carbon atoms is preferable, and for example, it can be obtained by dehydrating acetic acid, propionic acid, butyric acid, hexanoic acid, benzoic acid, etc. with glycols. it can.

Specific examples of monoethers or monoesters include:
Examples thereof include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monooctyl ether, polyethylene glycol monoacetate and polypropylene glycol monomethyl ether.

Since hydroxyl groups remain in these activity control agents, it is presumed that they react with the organoaluminum-based activator to alkoxylate the alkyl group of the activator, but by using these, one hour or more, Depending on the case, a long pot life of 10 hours or more can be achieved by adjusting the addition ratio. The activity control agent can be used in the same reaction system as the activator, but may be previously alkoxylated by prereacting both.

Use ratio of each component The activity regulator is usually 0.5 to 1 mol of the activator.
It is used in an amount of 2 mol, preferably 1 to 1.6 mol.
Since the effect of extending the pot life increases as the amount used increases, the length of the pot life can be arbitrarily adjusted by adjusting the addition ratio, etc.,
Excessive addition is not preferable because it tends to hinder the polymerization reactivity at high temperatures, although it is not as great as in the case of conventional alcohols.

The metathesis catalyst is usually about 0.01-50 mmol, preferably 0.1-10, relative to 1 mol of the norbornene-based monomer.
Used in the millimolar range. The activator (cocatalyst) is usually used in the range of 0.1 to 200 (molar ratio), preferably 2 to 10 (molar ratio) with respect to the catalyst component.

In addition to a catalyst, an activator and the above-mentioned activity modifier, halogenated hydrocarbons such as chloroform, carbon tetrachloride, hexachlorocyclopentadiene, etc.
No. 60-79035), or halides of tin tetrachloride, silicon tetrachloride, magnesium chloride, germanium chloride and the like may be used together. The amount of these used is not uniform depending on the kind, but is usually 5 mol or less, preferably 0.1 to 4 mol, per 1 mol of the active agent.

The metathesis catalyst, the activator and the activity modifier are preferably dissolved in the monomer before use, but may be suspended or dissolved in a small amount of solvent as long as the properties of the product are not substantially impaired. Good.

(Polymerization Conditions) In the present invention, a polymer is produced by a polymerization method in which a norbornene-based monomer is introduced into a mold having a predetermined shape and bulk polymerization is performed in the mold in the presence of a metathesis catalyst system. It suffices if it is substantially bulk polymerization, and a small amount of an inert solvent may be present.

In a preferred method for producing a polymer, a norbornene-based monomer is divided into two liquids and placed in another container, a metathesis catalyst is added to one, and an activator and an activity regulator are added to the other,
Two stable reaction solutions are prepared. The two types of reaction solutions are mixed and then poured into a molding die kept at a high temperature, where ring-opening polymerization by bulk is started to obtain a polymer.

In the present invention, a collision mixing apparatus conventionally known as a RIM molding apparatus can be used for mixing two types of reaction solutions. In this case, the containers containing the two types of reaction solutions serve as separate flow sources. Two kinds of flow
The mixing head of the RIM machine mixes instantaneously and then pours into a hot mold where it is immediately bulk polymerized to give the polymer.

Thus, although an impingement mixing device can be used, a feature of the invention is that it is not limited to such mixing means.
If the pot life at room temperature is longer than 1 hour, after mixing the two reaction solutions in a mixer, inject or inject the preheated mold once or several times. (For example, JP-A-59-51)
See 911). Compared with the impingement mixing device, this system is economical because the device can be downsized, and has an advantage that it can be operated at a low pressure.

Further, the present invention is not limited to the case of using two kinds of reaction solutions. As can be easily understood by those skilled in the art, various modifications are possible, for example, putting the reaction solution and the additive in the third container and using it as the third stream.

The mold temperature is 50 ° C or higher, preferably 60 to 200 ° C, particularly preferably 90 to 130 ° C. The mold temperature during the reaction is controlled by cooling as described later. Mold pressure is usually 0.1
Within the range of up to 100 Kg / cm ² .

The polymerization time may be appropriately selected, but is usually shorter than about 20 minutes, preferably 5 minutes or less, but may be longer than that.

The polymerization reaction components must be stored and operated under an atmosphere of an inert gas such as nitrogen gas. The molding die may or may not be sealed with an inert gas.

(Optional component) By incorporating various additives such as a filler, a pigment, a colorant, an antioxidant, a polymer modifier such as an elastomer or a dicyclopentadiene-based thermopolymer resin, the production method of the present invention can be achieved. The properties of the polymer can be modified.

The additives are mixed in advance with either one or both of the reaction solutions, or placed in the cavity of the mold.

Fillers include inorganic fillers such as glass, carbon black, talc, calcium carbonate and mica.

As antioxidants, there are various antioxidants for plastics and rubber such as phenol-based, phosphorus-based, amine-based and the like.
These antioxidants may be used alone or in combination. The blending ratio is 0.5% by weight or more, preferably 1 to 3% by weight based on the norbornene-based polymer.

Polymer modifiers include elastomers and thermopolymerized DCP resins. For example, blending an elastomer can increase the impact strength of the polymer, and blending a thermopolymerized DCP resin can further improve the flexural modulus. The polymer modifier is usually added to the reaction solution and dissolved before use.

As the elastomer, natural rubber, polybutadiene,
Polyisoprene, styrene-butadiene copolymer (SB
R), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene vinyl acetate copolymer (EV
A) and their hydrides.

If the reaction solution containing the monomer has a low viscosity by adding an elastomer or DCP-based thermopolymer resin,
The viscosity of the reaction solution can be adjusted to an appropriate value. Further, since these polymer modifiers lower the freezing point of the monomer reaction solution, the monomer reaction solution does not solidify even when a monomer having a high freezing point is used, and the operability in reaction injection molding is improved. On the contrary, when the viscosity of the monomer reaction solution is too low, it is possible to adjust the viscosity to an appropriate level by adding the dicyclopentadiene resin, so that the operability is similarly improved.

The blending ratio of these polymer modifiers can be appropriately determined,
100 parts by weight of polymer is normal for elastomers
0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, in the case of thermopolymerized DCP resin 0.5 to 150 parts by weight, preferably 20 to 5 parts by weight
0 parts by weight.

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. Parts and% are based on weight unless otherwise specified.

Example 1 Dicyclopentadiene (DCP) was placed in a container, to which diethylaluminum chloride (DEAC) was added at a concentration of 41 mmol, and the activity regulator shown in Table 1 was added at a concentration of 49.2 mmol or 57.4 mmol, respectively. Then A
A liquid was prepared.

On the other hand, tri (dodecyl) ammonium molybdate was added to DCP so as to have a concentration of 21 mmol, and this was designated as solution B.

Both reaction liquids have a space volume of 200 × 200 × 2 mm. 90 ° C
Using a gear pump and a power mixer, the mixture was mixed at a ratio of 1: 1 into a mold heated to 1, and the mixture was injected at almost normal pressure. The injection time was about 15 seconds. Thirty seconds after the end of the injection, heat was generated rapidly and the reaction started. Then, the reaction was performed in the mold for a total of 3 minutes. These series of operations were carried out under a nitrogen gas atmosphere.

Table 1 shows the pot lives when the kind of the activity regulator and the ratio to the active agent were changed. The glass transition temperature (Tg) and the flexural modulus of each of the obtained polymers were about 85 ° C. and 19,000 Kg / cm ² , and almost no difference was observed.

As is clear from Table 1, when the activity regulator of the present invention is used, the pot life is remarkably extended as compared with the conventional case where n-propyl alcohol or the like is used. In particular, the effect is remarkable in the case of a polyalkylene glycol-based activity regulator.

Example 2 Tungsten hexachloride and pt-butylphenol were added to toluene so that each had a molar concentration of 0.1, and nitrogen was bubbled to remove hydrogen chloride generated to prepare a catalyst component solution. Then dilute 3 times with DCP,
A catalyst component solution (A) (tungsten hexachloride 33 mmol concentration) was prepared.

DCP was placed in two containers, and to one of them, diethylaluminum chloride (DEAC) was added to DCP at a concentration of 48 mmol and triethylene glycol monomethyl ether at a concentration of 67.2 mmol, respectively.

On the other hand, the catalyst solution (A) was added to DCP so that the concentration of tungsten hexachloride was 7.0 mmol. Thereafter, a molded article was obtained in exactly the same manner as in Example 1. Reaction stock solution
The pot life at 25 ° C was 10 hours or more. The molded product has a glass transition temperature (Tg) of 80 ° C and a flexural modulus of 1
It was 8,000 Kg / cm ² .

Example 3 A molded article was obtained in exactly the same manner as in Example 1 except that ethylaluminum sesquichloride (EASC) was used as the activator (cocatalyst) and triethylene glycol monomethyl ether was used as the activity modifier at a concentration of 4.1 mmol. It was The pot life of the reaction stock solution was 6 hours or more. Also, the transition temperature (Tg) of the molded product is 80 ° C, and the flexural modulus is 18,0.
It was 00 Kg / cm ² .

Example 4 DCP and methyl tetracyclododecene (M
Experiments were performed with TD) or ethylidene tetracyclododecene (EDTD).

The monomers were placed in two containers, and to one of them, diethyl aluminum chloride (DEAC) was added at a concentration of 41 mmol, triethylene glycol monomethyl ether at a concentration of 57.4 mmol, and silicon tetrachloride at a concentration of 20 mmol.

On the other hand, tri (dodecyl) ammonium molybdate was added to the monomer at a concentration of 21 mmol. Thereafter, a molded article was obtained in exactly the same manner as in Example 1.
Table 2 shows the pot life time of the reaction stock solution at 25 ° C and the physical properties of the molded product.

EFFECTS OF THE INVENTION According to the present invention, in bulk polymerization using a metathesis catalyst system of a norbornene-based monomer, the pot life of the reaction stock solution could be significantly extended without impairing the polymerization activity.

As a result, a large amount of force is not required for mixing the reaction solution containing the catalyst and the activator, and the injection into the mold can be performed at a low pressure. Conventionally, the mixing method was difficult except for the collision mixing method. On the other hand, it becomes possible to easily perform a method of injecting or injecting into a preheated mold once or several times after completing the mixing of two kinds of reaction solutions in a mixer in advance. It can be miniaturized, can be operated at low pressure, and has an excellent effect of being economical.

Claims (1)

[Claims] 1. A bulk polymerization of a norbornene-based monomer in the presence of a metathesis catalyst system consisting essentially of a tungsten-based or molybdenum-based catalyst (A), an organoaluminum-based activator (B) and an activity modifier (C). In the method of producing a norbornene-based polymer, a monoether and / or a monoester of at least one glycol compound selected from alkylene glycols and polyalkylene glycols is used as the activity modifier (C). Manufacturing method.