JPH0229423A - Manufacture of colored norbornene polymer - Google Patents

Abstract

PURPOSE:To produce the title polymer which is colored uniformly by carrying out bulk polymerization in a mold in the presence of a specific catalyst system using as a mother coloring liquor a dispersion prepared by homogenizing a mixture of a norbornene monomer and a colorant with a homogenizer. CONSTITUTION:When a norbornene monomer (e.g. dicyclopentadiene) is subjected to bulk polymerization in a mold in the presence of a colorant (e.g. carbon black or TiO2) and a metathesis catalyst system (e.g. an organic ammonium salt), a dispersion prepared by homogenizing a mixture of the norbornene monomer and the colorant with a homogenizer is used as a mother liquor for coloring. According to this process, the dispersibility of the colorant is improved, thereby allowing a uniformly colored norbornene polymer to be obtained. Also, a colored molded product which is good in physical properties can be obtained without causing obstruction of polymerization.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing norbornene-based polymers by bulk polymerization in a mold, and more specifically relates to a method for producing norbornene-based polymers that are uniformly colored without uneven coloring. Concerning the manufacturing method.

(Prior art) Bulk polymerization of norbornene monomers such as dicyclopentadiene (abbreviated as DCP) and methyltetracyclododecene (abbreviated as MTD) in a mold in the presence of a metathesis catalyst system; It is known to add inorganic pigments such as carbon black and titanium dioxide to obtain colored polymers.

For example, JP-A-58-129013 discloses a method for producing a thermosetting DCP homopolymer by reaction injection molding (RIM) using a metathesis catalyst system, and in a preferred embodiment, The homopolymer consists of one solution consisting of a mixture of DCP and a catalyst component of a metathesis catalyst system, such as tungsten halide, and the other solution consisting of DCP and an activator of a metathesis catalyst system, such as aluminum halide. It is produced by mixing two solutions in the mixing head of a reaction injection molding machine (RIM machine) and then injecting them into a mold. At that time, it has been suggested that fillers such as carbon black are added.

Jikai No. 59-51911 discloses RIM of cyclic olefins containing norbornene rings such as DCP and MTD, and also in this bulk polymerization method, it is indicated that pigments such as titanium dioxide are added. There is.

In these conventional methods, inorganic pigments are simply mixed with norbornene monomers, but with these methods, inorganic pigments easily form mako (
This causes poor dispersion and causes sedimentation during storage of the reaction stock solution.

Such defects can be improved by mixing and dissolving an inorganic pigment in a parabolic norbornene monomer obtained by kneading the inorganic pigment with an elastomer in advance. However, this method
There are problems in that it may cause deterioration of the inorganic pigment itself that is produced during kneading, or it cannot be applied to carbonaceous pigments that are sensitive to heat.Furthermore, the amount of inorganic pigment added depends on the elastomer. Therefore, there is a drawback that it is limited by the blending ratio of the elastomer to the norbornene monomer.

Organic pigments have the same problems as inorganic pigments, but
In the case of organic pigments, it is particularly difficult to apply the kneading method with elastomers because they are easily discolored by heat.

If a colorant such as an inorganic pigment or an organic pigment is poorly dispersed in a stock solution, the resulting norbornene polymer will be unevenly colored and heterogeneous - and the colorant will generally inhibit the polymerization of the norbornene monomer. There is a need for a solution to this problem, as it prolongs the molding time and lowers the secondary transition temperature of the resulting polymer.Furthermore,
At present, there are many problems with the coloring of norbornene-based polymers, such as staining of reaction stock solution storage tanks with colorants and color contamination when changing colors.

(Problems to be Solved by the Invention) An object of the present invention is to obtain a uniformly colored norbornene-based polymer with no uneven coloring by a bulk polymerization method of a norbornene-based monomer in a mold.

Another object of the present invention is to prevent polymerization inhibition caused by colorants,
The objective is to obtain a norbornene polymer with good physical properties.

The present inventors have worked diligently to develop a method that can overcome the problems of the prior art and obtain a norbornene-based polymer with no color unevenness without being limited by the type of colorant. As a result, they discovered that it is effective to use a coloring mother liquor in which a colorant is uniformly dispersed in a norbornene monomer using a high-speed dispersion machine such as a homogenizer, and based on this knowledge, they have completed the present invention. .

(Means for Solving the Problems) Thus, according to the present invention, when bulk polymerizing a norbornene monomer in a mold in the presence of a colorant and a metathesis catalyst system, a mixture of a norbornene monomer and a colorant is preliminarily prepared in a homogenizer. Provided is a method for producing a colored norbornene-based polymer, characterized in that a dispersion prepared by homogenization is used as a coloring mother liquor.

Furthermore, in the present invention, by using a mixture of a norbornene monomer and a coloring agent homogenized with a homogenizer and then removing a low boiling point fraction as the mother liquor for coloring, there is no inhibition of polymerization and uniform coloring is achieved. , a molded article (norbornene polymer) with good physical properties can be obtained.

Furthermore, if the homogenized coloring mother liquor (C) is used as a third stream in the reaction stock solution (A) containing the metathesis catalyst and the reaction stock solution (B) containing the activator, polymerization will not be inhibited, and
A desired colored product can be easily obtained by switching the mother liquor for coloring, and the problem of fouling of the reaction stock solution storage tank can also be solved.

Hereinafter, the constituent elements of the present invention will be explained in detail.

(Norbornene monomer) The norbornene monomer used in the production method of the present invention is substituted or unsubstituted bicyclic or more polycyclic norbornene, and specific monomers include 2-norbornene, 5 - Bicyclics such as methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenylnorbornene, Bicyclics such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, medyltetracyclododecene, ethyltetracyclododecene, dimethyltetracyclododecene, ethylidene l-lacyclododecene, phenyltetracyclododecene Examples include tetracyclics such as , bicyclics such as tricyclopentadiene, and heptacyclics such as tetracyclopentadiene. These norbornene monomers can be used alone or in combination of two or more.

Among these, bicyclics and bicyclics are preferred from the viewpoint of ease of handling, reactivity, heat resistance, etc.

In the present invention, the polymer produced using the crosslinking monomer can be thermosetting. The crosslinkable monomer is a polycyclic norbornene monomer having two or more reactive double bonds, and specific examples include dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. Therefore, when the norbornene monomer and the crosslinking monomer are the same, there is no need to use any other crosslinking monomer.

Norbornene monomers having two or more rings can also be obtained by heat-treating dicyclopentadiene. Examples of the heat treatment conditions include heating dicyclopentadiene in an inert gas atmosphere at a temperature of 120 to 250° C. for 0.5 to 20 hours. This heat treatment yields a monomer mixture containing tricyclopentadiene and unreacted dicyclopentadiene.

Furthermore, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, which can undergo ring-opening polymerization together with one or more of the norbornene monomers mentioned above, may be used in combination without impairing the purpose of the present invention. You can do it.

(Metathesis Catalyst System) The catalyst used in the present invention may be any metathesis catalyst system known as a catalyst for ring-opening polymerization of norbornene monomers (for example, JP-A-58-127728, JP-A-58-129013). , No. 59-51911, No. 60
-79035, 60-186511, 61-1
No. 26115, etc.), there are no particular restrictions.

Specific examples of metathesis catalysts include halides, oxyhalides, oxides, and organic ammonium salts of tungsten, molybdenum, and tantalum; suitable examples include tungsten hexachloride, tungsten oxytetrachloride, and tungsten oxide. Tungsten compounds such as , tridodecyl ammonium kungesteate, tri(tridecyl) ammonium tungstate 1, trioctylammonium kungeste 1~; molybdenum pentachloride, molybdenum oxytrichloride, tridodecyl ammonium molybdate, methyltricaprylammonium Examples include molybdenum compounds such as mumolybdate, tri(tridecyl)ammonium molybdate, and trioctyl ammonium molybdate; and tanker compounds such as tanker pentachloride. Among these, it is preferable to use a catalyst that is soluble in the norbornene monomer used in the reaction, and from this point of view, organic ammonium salts are preferred.

When the metathesis catalyst is a halide, the catalyst can be solubilized in the norbornene monomer by prior treatment with an alcohol compound or a phenol compound. Further, if necessary, a Lewis base such as benzonitrile or tetrahydrofuran, or a chelating agent such as acetylacetone or acetoacetic acid alkyl ester may be used in combination, thereby preventing premature polymerization.

Examples of the activator (cocatalyst) include alkyl aluminum halides, alkoxyalkylaluminum halides, aryloxyalkylaluminum halides, organotin compounds, and suitable examples include ethyl aluminum dichloride, diethylaluminum dichloride, ethyl Examples include aluminum sesquichloride, diethylaluminum iodide, methylaluminum sesquichloride, tetrabutyltin, and pre-reaction products of alkylaluminum halides and alcohols.

Among the activators, alkoxyalkylaluminum halides and aryloxyalkylaluminum halides have a moderate bott life at room temperature even when mixed with catalyst components, so they are advantageous in operation (for example, in JP-A-Sho). No. 59-51911). In the case of alkylaluminum halides, there is a problem that polymerization starts immediately when a catalyst is mixed, but in that case, ethers,
The initiation of polymerization can be controlled by the combined use of activity regulators such as esters, ketone necks, nitriles, and alcohols.

(For example, JP-A-58-129013, JP-A No. 61120
No. 814) In addition to catalysts and activators, halogenated hydrocarbons such as chloroform and carbon tetrachloride (for example, JP-A No. 60-79
No. 035), or halides such as tin tetrachloride, silicon tetrachloride, tetrachloride if), germanium tetrachloride, and magnesium chloride may be used in combination. These are usually activators 1
It is used in a proportion of 15 mol or less, preferably 0.1 to 4 mol per mole.

The amount of the metathesis catalyst is usually about 0.01 to 50 mmol, preferably 0.01 to 50 mmol per mol of the norbornene monomer.
．． It is used in a range of 1 to 10 mmol. The activator (cocatalyst) is generally used in an amount of 0.1 to 200 (mole ratio), preferably 2 to 10 (mole ratio), based on the catalyst component.

Both the metathesis catalyst and the activator are preferably used after being dissolved in a monomer, but they may also be used after being suspended or dissolved in a small amount of a solvent as long as the properties of the product are not essentially impaired.

(Coloring agent) The coloring agent used in the present invention contains an insoluble component in the monomer, and may be an inorganic pigment, an organic pigment, or a mixture thereof.

Specific examples of inorganic pigments include carbon black, graphite, yellow lead, iron oxide yellow, titanium dioxide, zinc oxide, ferric oxide, dilead tetroxide, red lead, chrome green, and navy blue. Various types of carbon black can be used, including furnace method, channel method, thermal method carbon black, and acetylene black.

Examples of organic pigments insoluble in monomers include Benzidine Yellow, Cromophthal Elo-6G, Cromophthal Elo-3G, Cromophthal Elo-R, and the like.

Pigments may be used in combinations of various types (inorganic pigments/inorganic pigments, organic pigments/organic pigments, inorganic pigments/organic pigments, etc.). , a pigment soluble in the monomer may be used as its component.

As a specific example, two or more types of inorganic pigments may be mixed and used, for example, a gray pigment is obtained by mixing a small amount of carbon black (black) with titanium oxide (white). In addition, inorganic pigments and organic pigments may be used in combination, such as red with titanium white and quinacridone, yellow with titanium white and polyazo, green with titanium white and cyanine green, blue with titanium white and cyanine blue, etc. .

The proportion of pigment used depends on the level of hiding power, but usually
10% by weight or less of the total amount with norbornene monomer,
Preferably it is 0.1 to 7% by weight.

(Homogenizer) The homogenizer used in the present invention can be any machine that can apply high-speed forced convection action to the pigment in order to uniformly disperse (homogenize) the pigment, which is a coloring agent, in the norbornene monomer. There is no restriction on the model, but for shooting purposes, the rotation speed is 1,000 rpm to 100,00 rpm.
m, preferably 200 Orpm to 20. OOOrpm
A high-speed disperser with a rotational capacity of

The convection of the homogenizer is effective against carbon black, etc.
Convection flows from the upper layer to the lower layer for pigments that easily float in the monomer, and convection flows from the lower layer to the -L layer for pigments that tend to settle in the monomer, such as titanium white. desirable.

Specific equipment includes a general homogenizer that features a strong shear flow in the radial direction of the tank; In addition to the homodisper used, there is also a pipeline homogenizer that features strong shear, impact, and turbulence using a high-speed homomixer type turbine and stator.In the present invention, these are collectively referred to as a homogenizer.

There is no particular limit to the 41 degrees of the pigment dispersed in the norbornene monomer (it can be determined as appropriate depending on the amount of pigment to be contained in the molded article (norbornene polymer), but from the viewpoint of work efficiency, Usually, it is added and dispersed to a concentration of 5 to 50% by weight, preferably 10 to 4.0% by weight, and the resulting coloring mother liquor is diluted with a monomer as appropriate before use.

Although the dispersion time varies slightly depending on the type of pigment in terms of its compatibility with the monomer, in most cases uniform dispersion can be achieved within 30 minutes. At this time, if this is carried out while blowing an inert gas such as nitrogen into the dispersion tank, there is no fear of contamination with catalyst-deactivating components, and the operation can be performed safely.

Furthermore, since colorants often contain components that deactivate catalysts and activators, it is preferable to remove the deactivated components before mixing with monomers. As a method for removing the deactivated components, there is a method of removing low-boiling components from the coloring mother liquor homogenized using a homogenizer. For this purpose, the initial distillation cut method and treatment with an activator can be cited.

The initial cut method usually has a pressure kerf of 50 to 100010
0O, preferably -730~200mm Hg, bottom temperature 50℃~130''C1, preferably 70℃~110
This is a method in which components flowing out are cut under the condition of .degree. C., and the amount to be cut is usually 1 to 10% by weight, preferably 1 to 5% by weight of O of the charged amount.

(Polymerization Conditions) In the present invention, a norbornene-based polymer, that is, a molded article, is produced by a method in which a norbornene-based monomer is introduced into a mold of a predetermined shape and polymerized in bulk in the presence of a metathesis catalyst system.

When bulk polymerizing norbornene monomers in the presence of a metathesis catalyst system, two types of reaction stock solutions are usually prepared. That is, put the activator in one container (Ai night),
A catalyst component is placed in the other container (B?Fi), and a norbornene monomer is added to each reaction stock solution.

These two kinds of reaction stock solutions are mixed and then poured into a mold, where ring-opening polymerization is carried out in bulk to obtain a molded article.

The solution obtained by dispersing the coloring agent in the norbornene monomer may be used as it is as a monomer stock solution, but in order to use a homogenizer efficiently, usually a coloring mother liquor containing a coloring agent with a high concentration is used. Use by diluting with norbornene monomer. In that case, if the coloring mother liquor is added to Solution A, the activity of the catalyst will decrease and polymerization will be inhibited.
It is desirable to add it only to liquid B.

In the present invention, it is possible to use an impingement mixing device for mixing both reaction stock solutions A and B, but in cases where the pot life at room temperature is more than 1 hour,
Two types of reaction stock solutions can be mixed in a mixer such as a static mixer or a power mixer, and then injected or injected into a mold once or a predetermined number of times (for example, see JP-A-59-51911). )
. Moreover, a mixture of both reaction stock solutions can also be continuously supplied into a molding die. In the case of this method, the device can be made smaller compared to the collisional mixer, and
It has the advantage of being able to operate at low pressure.

Also, in the present invention, the coloring mother liquor can be placed in a third container and used as a third stream. According to this method, since the reaction stock solution does not contain a coloring agent, the storage tank can be prevented from becoming dirty, and the operation when changing the color by changing the product type is also simple. Furthermore, since the mixture of colorant and monomer is homogenized and stored in the absence of a metathesis catalyst system, the catalyst There is no decrease in activity and polymerization inhibition is unlikely to occur.

As a result, the curing time can be shortened, and a molded article with good surface properties and a higher glass transition point can be obtained.

The mold temperature is usually 30'C or higher, preferably 40-2
00°C5 Particularly preferably 50 to 130°C.

The polymerization time may be selected as appropriate, but is usually shorter than about 20 minutes (preferably 5 minutes or less, but may be longer).

(Optional Components) The properties of the molded article of the present invention can be modified by blending various additives such as fillers, antioxidants, hydrogenated dicyclopentadiene thermopolymer resins, and elastomers. The additives are used by being mixed in advance with one or both of the reaction stock solutions.

As antioxidants, there are various types of antioxidants for glass and rubber, such as phenol-based, phosphorus-based, and amine-based antioxidants.

Metal stabilizers such as zinc stearate, lead salicylate, cadmium benzoate, calcium salts, and aluminum salts can also be used to prevent discoloration and improve weather resistance.

Elastomers are added to improve impact resistance and prevent pigments from settling. Examples of elastomers include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene-butadiene copolymer (SBR). Examples include propylene-dienecoupolymer (EPDM), ethylene vinyl acetate copolymer (EVA), and hydrides thereof. Are there two or more types of these elastomers? It can also be used commensurately.

The blending ratio of the elastomer can be determined as appropriate depending on the molecular weight of the elastomer and the desired viscosity of the reaction liquid, but it is usually 10% by weight or less, preferably 1 to 8% by weight.
It is.

(Example) The present invention will be described in more detail with reference to Examples below. In addition, parts and percentages in Examples, Comparative Examples, and Reference Examples are as follows:
Unless otherwise specified, these are important criteria.

Example 1 (Preparation of mother liquor for coloring) In order to confirm the dispersibility of the pigment in the norbornene monomer, a sedimentation test of the pigment was conducted.

Styrene-isoprene-styrene block copolymer (SIS) (
5 parts of FinTac 3420 (trade name, Nippon Zeon Co., Ltd.) and 30 parts of various pigments shown in Table 1 were added and mixed. As a mixing method, homogenization method using a homogenizer (6
000 rpm for 30 minutes, experiment numbers 1 to 6), and for comparison, a method using a normal stirrer (30 minutes at too rpm).
Stirring for a minute, experiment numbers 7 to 8) was employed.

After mixing, the coloring mother liquors of experiment numbers 1 to 4 were distilled under conditions of a coloring mother liquor temperature of 80°C and a degree of vacuum of -710 mmHg to remove 2% of the charge as a low boiling point fraction. On the other hand, experiments Nos. 5 and 6 showed those without initial cutting.

The results are shown in Table 1, and when the homogenizer was used for dispersion (experiment numbers 1 to 6), the dispersion was uniform and there was no sedimentation over time. When dispersing using a normal stirrer (experiment numbers 7 to 8), the pigment tends to become lumpy;
A sedimentation phenomenon was also observed.

The pigments used are as follows.

Carbon black/Mitsubishi Kasei (Φ# 1000 Titanium White: Dainichiseika (White-8 Quinacridone 2 Dainichiseika (t$) TSD-T-120Red Polyazo
Two major Nichisei Chemical (m TSD-P-420 Yellow homogenizers (dispersing machines) used Homomixer M type for Tokushu Kika Kogyo ①.

(Left below) Oiba ■Yu (Production of colored polymer, three-component type) Add 100 parts of dicyclopentadiene (DCP) to styrene-isoprene-styrene block copolymer (SIS) (FinTac 3420, Nippon Zeon Co., Ltd. product) Add 5 parts of (name) and mix. This solution was placed in two containers, and one contained diethylaluminum chloride (DEAC) at a concentration of 4.1 mmol, n-propyl alcohol at a concentration of 4.1 mmol, and silicon tetrachloride at a concentration of 2.1 mmol relative to DCP. (Liquid A). On the other hand, for DCP,
Tri(tridecyl)ammonium molybdate was added to a concentration of 1 mmol (solution B).

The two reaction solutions containing the metathesis catalyst system and the coloring mother liquors (liquid C) of experiment numbers 1 to 6 of Example 1 were combined into liquid A/B.
The liquid mixture was mixed with a three-component mixing power mixer at a mixing ratio of liquid/C liquid of 1/110.095 (pigment concentration 1.4%), and then each mixed liquid was heated to 70°C in a space volume of 200 mm x 200 mm x 3 mm. It was quickly injected into the mold at almost normal pressure using a gear pump and a power mixer. After the system rapidly generated heat, the reaction was continued for 3 minutes to obtain a molded DCP polymer. Table 2 shows the appearance and physical properties of the molded product obtained.

When the mother liquor for coloring of the present invention is used, uniformly colored molded products can be obtained.

In addition, when using a coloring mother liquor with initial distillation cut (experiment numbers 9 to 12), the Tg of the DCP polymer is higher than when using a coloring mother liquor without initial distillation cut (experiment numbers 13 to 14). , Also, the time until heat generation (molding time)
It turns out that it is also short.

On the other hand, a similar experiment was attempted using coloring mother liquors (coloring mother liquors G and H) that were dispersed using a regular stirrer, but due to uneven dispersion of the coloring mother liquors, color unevenness occurred and the product was damaged. They could only produce products of low value.

(Left below) Add 100 parts of dicyclopentadiene (DCP) to 100 parts of dicyclopentadiene (DCP), styrene-isoprene-styrene block copolymer (SIS) (FinTac 3420, Nippon Zeon Co., Ltd. product) 10 parts of each of the colored mother liquors of experiment numbers 1 to 8 of Example 1 were added and mixed. Pour this mixture into two containers, one containing
Diethylaluminum chloride (DEAC) for DCP
) was added at a concentration of 4.1 mmol, n-propyl alcohol at a concentration of 4.1 mmol, and silicon tetrachloride at a concentration of 2.1 mmol (solution A). On the other hand,
Tri(tridecyl)ammonium molybdate was added to DCP at a concentration of 1 mmolar (B?
& ).

Both reaction solutions were rapidly injected into a mold having a space volume of 200 mm x 200 mm x 3 mm and heated to 70° C. at approximately normal pressure using a Heger pump and a power mixer.

After rapidly generating heat, the reaction continued for 3 minutes, resulting in molded product D.
A CP polymer was obtained. Table 3 shows the appearance and physical properties of the molded product obtained.

It can be seen that while the conventional method resulted in uneven coloring, the present invention yielded molded articles that were uniformly colored and also had excellent impact resistance.

Although the time required to generate heat is slightly longer than in Example 2 (three-component type), it is still approximately the same as the conventional method. In addition, when a similar experiment was conducted by adding the coloring mother liquor only to Solution B, the time until heat generation was significantly shortened, and Example 2 (
The results were almost the same as those of the three-component type.

(Hereinafter in the margin) (Effects of the invention) Thus, according to the present invention, the dispersibility of the colorant is improved,
As a result, a uniformly colored norbornene-based polymer without uneven coloring can be obtained.

Further, according to the present invention, a colored molded article with good physical properties can be obtained without causing polymerization inhibition.

Claims (4)

[Claims] (1) When bulk polymerizing norbornene monomers in a mold in the presence of a coloring agent and a metathesis catalyst system, a dispersion prepared by homogenizing a mixture of norbornene monomers and coloring agents with a homogenizer is used as a coloring mother liquor. A method for producing a colored norbornene-based polymer, characterized in that it is used. (2) The method for producing a colored norbornene polymer according to claim 1, wherein the coloring mother liquor is obtained by homogenizing a mixture of a norbornene monomer and a colorant using a homogenizer, and then removing a low boiling point fraction. (3) A reaction stock solution containing a norbornene monomer and an activator (A), a reaction stock solution containing a norbornene monomer and a metathesis catalyst (B), and a coloring mother liquor (C) obtained by homogenizing a mixture of a norbornene monomer and a colorant using a homogenizer. ) as independent streams, or the above (B
1. A method for producing a colored norbornene-based polymer, which comprises mixing a mixed solution of ) and (C) with (A), supplying the mixture into a mold, and polymerizing in bulk within the mold. (4) A coloring mother liquor obtained by homogenizing a mixture of a norbornene monomer and a coloring agent using a homogenizer and then removing a low boiling point fraction.