JPH0857930A - Method of extrusion-molding polycyanoarylether - Google Patents

Abstract

PURPOSE: To enable high quality polycyanoarylether extrusion-moded items to be mass-produced with improved productivity by supplying specific polycyanoarylether into the cylinder of an extrusion molding machine in order to be a given supply rate, and to then be subjected to extrusion molding. CONSTITUTION: Polycyanoarylether is used which contains at least a 50mol% repeating unit indicated in the formula and has a reduced viscosity [ηSD/c] of 0.5-3 deciliter in a solution of 0.2g/deciliter concentration at 60 deg.C having P-chlorophenol as a solve. The specific polycyanoarylether is supplied into the cylinder of an extrusion molding machine in order that a supplying amount rate indicated by an equality of supply rate = supply quantity/theoretical extrusion quantity becomes 0.2-0.6. In addition. It is preferred to use a ceramic-coated surface screw for the screw of an extrusion molding machine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for extrusion-molding a polycyanoaryl ether, and more specifically, it suppresses the decomposition of the polycyanoaryl ether during extrusion to reduce the molecular weight of the polycyanoaryl ether, while suppressing the screw torque. Polycyanoaryl ether can be extruded in a state where the fluctuation rate of the extrusion rate is kept low, and it has various properties such as transparency, heat resistance, chemical resistance, flame retardancy, mechanical properties, and electrical properties. The present invention relates to a method capable of mass-producing an extruded product of a high-quality polycyanoaryl ether which is excellent and can be suitably used in various fields such as the electric / electronic device field, the automobile field, and the aerospace field with high productivity.

[0002]

2. Description of the Related Art In recent years, thermoplastic resin moldings have been mass-produced in various fields. Most of these molded products are landfilled in the soil without being reused after use. However, this landfill treatment is one of the causes of global environmental pollution, which is a serious social problem. Moreover, the disposable use of such a molded article is against the effective use of limited resources.
Therefore, some molded articles of thermoplastic resin having recyclability and capable of contributing to environmental protection have been developed. Among the above-mentioned thermoplastic resins, polycyanoaryl ether is excellent in various properties such as transparency, heat resistance, chemical resistance, flame retardancy, mechanical properties, and electrical properties. Is expected to be applied.

By the way, in the prior art, for example, JP-A-63-001524 and JP-A-3-122130.
As disclosed in the publication, an extrusion molded article of the polycyanoaryl ether was obtained by a general extrusion molding method.

However, in the case of the conventional extrusion molding method, since the screw torque is large, the productivity is low, and the variation rate of the extrusion amount is large, the extrusion molding of high quality polycyanoaryl ether is mass-produced with high productivity. There is a problem that you can not. It is also conceivable to raise the temperature of the extruder in order to improve the moldability and productivity, but in this case, the polycyanoaryl ether decomposes during extrusion. As a result, there is a problem that the molecular weight of the polycyanoaryl ether is lowered and various characteristics such as mechanical strength of the extrusion molded product are deteriorated.

An object of the present invention is to solve the above conventional problems. The present invention extrudes a polycyanoaryl ether in a state where the screw torque and the variation rate of the extrusion amount are suppressed to a low level while suppressing a decrease in the molecular weight of the polycyanoaryl ether which is decomposed during the extrusion process. It is possible to obtain a high-quality extruded product of polycyanoaryl ether, which has the above-mentioned excellent properties and can be suitably used in various fields such as electric / electronic equipment fields, automobile fields, aerospace fields, etc. with high productivity. , The purpose is to provide a method that can be mass-produced.

[0006]

In order to achieve the above object, the present invention comprises a repeating unit represented by Chemical Formula 1 at least 50 mol% and a concentration of 0.2 g / p-chlorophenol as a solvent. A polycyanoaryl ether having a reduced viscosity [η _sp / c] of 0.5 to 3 deciliter / g at 60 ° C. in a solution of decyl is introduced into a cylinder of an extruder by the following formula: feed rate = feed rate / theoretical extrusion rate Is a method for extrusion-molding a polycyanoaryl ether, wherein the extrusion-molding is performed while supplying the mixture at a supply rate of 0.2 to 0.6.

[0007]

Embedded image

Next, the preferred embodiments of the present invention will be described.
For example, the extrusion molding method of the polycyanoaryl ether according to claim 1, wherein a screw whose surface is coated with a ceramic is used as the screw in the extruder, wherein the ceramic is a metal carbide, a metal nitride or a metal. It is an extrusion molding method of the polycyano aryl ether according to claim 2, which is at least one selected from the group consisting of carbonitrides, and the extrusion molding temperature is 340 to 400 ° C. Is an extrusion molding method of polycyanoaryl ether of
The extrusion molding method for polycyanoaryl ether according to claim 1, wherein the supply rate is 0.2 to 0.6,
The extrusion molding method for polycyanoaryl ether according to claim 1, wherein the reduced viscosity [η _sp / c] is 0.7 to 2.5 deciliter / g.

The present invention will be described in detail below.

In the extrusion molding method of polycyanoaryl ether of the present invention, a specific polycyanoaryl ether is extruded while being supplied to a cylinder of an extruder at a specific supply rate.

(1) Polycyanoaryl ether As the polycyanoaryl ether, the repeating unit shown in Chemical formula 1 is usually contained in an amount of 50 mol% or more, preferably 80 to 100 mol%, and further 90 to 100 mol%. Is preferred. Among these, homopolymers containing 100 mol% of the repeating unit shown in Chemical formula 1 are preferable.

The specific structure of the repeating unit shown in Chemical formula 1 is not particularly limited and may be appropriately selected depending on the intended purpose. In the present invention, the repeating unit shown in Chemical formula 2 is preferable.

[0013]

Embedded image

The polycyanoaryl ether used in the present invention may contain one kind or two or more kinds of other repeating units in a ratio of less than 50 mol% in addition to the repeating unit shown in the chemical formula 1. . The other repeating unit is 5
When it is less than 0 mol%, the characteristics of the polycyanoaryl ether are not impaired.

Suitable examples of the other repeating unit include polycyanoaryl ethers represented by Chemical formula 3, Chemical formula 14, Chemical formula 15, Chemical formula 16 and the like.

[0016]

[Chemical 3]

(In the formula, Ar means the structures shown in Chemical formulas 4 to 13)

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

Embedded image

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

Embedded image

[0029]

[Chemical 15]

[0030]

Embedded image

Among these, chemical formula 4, chemical formula 8, chemical formula 9, chemical formula 1
The structure shown in 0 is preferable. In the case of the structure shown in Chemical formula 10, the structure shown in Chemical formula 17 is particularly preferable.

[0032]

[Chemical 17]

The terminal of the polycyanoaryl ether used in the present invention has, for example, a hydrogen atom, an alkyl group such as a methyl group, or a group shown in Chemical formula 18, Chemical formula 19, Chemical formula 20 or Chemical formula 21.

[0034]

Embedded image

[0035]

[Chemical 19]

[0036]

Embedded image

[0037]

[Chemical 21]

Among these, the structures represented by hydrogen atom and methyl group are preferable.

The polycyanoaryl ether is 0.2
The reduced viscosity [η _sp / c] at 60 ° C. of a solution prepared by dissolving p-chlorophenol in a concentration of g / deciliter is usually 0.5 to 3 g / deciliter, preferably 0.7 to 2.5 g / deciliter. When the reduced viscosity [η _sp / c] is within the above range,
Sufficient properties such as mechanical strength and heat resistance of the extruded product can be obtained, and since the melt viscosity is appropriate, extrusion molding is easy, which is preferable.

-Production of Polycyanoaryl Ether- The polycyanoaryl ether may be, for example,
Can be produced by polymerizing dihalogenobenzonitrile and resorcinol shown in 1) in approximately equimolar amounts in the presence of an alkali metal carbonate in an aprotic polar solvent in an inert gas atmosphere.

[0041]

[Chemical formula 22]

(In the formula, X and X'represent a halogen atom, which may be the same or different from each other.) Examples of the dihalogenobenzonitrile include:
2,6-dihalogenobenzonitrile, 2,4-dihalogenobenzonitrile and the like can be mentioned. Among these, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-dichlorobenzonitrile and 2,4-difluorobenzonitrile are preferable,
Particularly, 2,6-dichlorobenzonitrile is preferable.

As the alkali metal carbonate, it is sufficient that the resorcin can be converted into an alkali metal salt,
Although not particularly limited, examples thereof include carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, rubidium carbonate, and hydrogen carbonates corresponding thereto. Among these, sodium carbonate, potassium carbonate, and hydrogen carbonate corresponding to these are preferable.

The amount of the alkali metal carbonate to be used can be appropriately selected depending on the situation, and is usually 1.0 to 1.3 times equivalent to the resorcin, and particularly slightly excessive amount. preferable.

Examples of the aprotic polar solvent include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N.
-Diethylacetamide, N, N-dipropylacetamide, N, N-dimethylbenzoic acid amide, N-methyl-
2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n
-Butyl-2-pyrrolidone, N-cyclohexyl-2-
Pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-
Methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-
6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N , N'-dimethylimidazolidinone, 1,
Examples thereof include 3-dimethylimidazolidinone and diphenyl sulfone. Among these, N-methyl-2-pyrrolidone is preferable.

The aprotic polar solvent may be used in an amount sufficient to dissolve the compound shown in Chemical formula 3 and resorcin.

Examples of the inert gas include argon gas and nitrogen gas.

In the present invention, a chain extender or a terminal terminator such as fluorobenzonitrile may be appropriately added before the initiation of the polymerization reaction or during the polymerization reaction.

The conditions of the polymerization reaction cannot be unconditionally determined because it depends on the type of dihalogenobenzonitrile used and the like, but the reaction temperature is usually 200 ° C. or higher and 2
The temperature is preferably 00 to 210 ° C. The reaction time is usually 2 to 6 hours, preferably 2 to 5 hours.

As an example of the production of the polycyanoaryl ether, for example, the polycyanoaryl ether containing the repeating units shown in Chemical formulas 1 and 2 is a part of the resorcinol (usually 50 mol%) to be used. (Less than 1) instead of the divalent phenol corresponding to the repeating unit shown in Chemical Formula 2 above, and reacting in the same manner.

The polycyanoaryl ether may be a homopolymer having the repeating unit shown in Chemical formula 1 or a heteropolymer.

The polycyanoaryl ether obtained by the polymerization reaction contains a small amount of the alkali metal salt. The content is usually preferably 50 ppm or less. When the content is 50 ppm or less, even if the extruded product of polycyanoaryl ether is used in various devices for a long period of time, the metal portion around it will not be corroded.

To reduce the amount of the alkali metal salt,
The polycyanoaryl ether is preferably washed with an acidic aqueous solution containing an organic acid or an inorganic acid and adjusted to pH 3.5 or less.

Examples of the organic acid include formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid,
Examples thereof include monocarboxylic acids such as propionic acid and dicarboxylic acids such as oxalic acid and malonic acid. Among these, dicarboxylic acids such as oxalic acid are preferable, and oxalic acid is particularly preferable. These may be used alone,
Alternatively, two or more kinds may be used in combination.

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Of these, hydrochloric acid is preferred. These may be used alone or in combination of two or more.

The time for washing the polycyanoaryl ether with the acidic aqueous solution is not particularly limited as long as it is a time sufficient to reduce the content of the alkali metal salt to 50 ppm or less. In order to accelerate the desalting effect by washing, a mixture of an acidic aqueous solution and polycyanoaryl ether may be heated or heated under pressure during washing.

After washing with the above acidic aqueous solution, pure water, in order to remove the acid from the polycyanoaryl ether,
It is preferable to thoroughly wash with ion-exchanged water, distilled water or the like.

(2) Supply of Polycyanoaryl Ether to Cylinder of Extrusion Molding Machine The extrusion molding machine is not particularly limited, and there are known extrusion molding machines such as a single screw extruder and a twin screw extruder. Can be appropriately selected and used. In the present invention, of these, it is preferable to use a uniaxial extruder in which the variation rate of the extrusion amount is small and the uniformity of the thickness, quality and the like of the extrusion molded product can be easily controlled.

Examples of the shape of the screw in the extruder include constant pitch variable depth type, variable depth constant depth type, variable pitch variable depth type, metalling type, gradually increasing valley diameter type, torpedo and darmedge type. it can. Examples of the structure of the screw include a general-purpose type, a full flight type, and a Maddock (Maddo).
ck) type, Mailerfer type, bubble flight type and the like. Examples of the structure of the mixing part of the screw include dullage type, wave type, unimelt type, pin type, H type.
Examples thereof include M type, DIS type and BM type. Among these, if a full flight type screw is used, the self-cleaning property in the extruder is good,
This is preferable because the variation rate of the extrusion rate is small. Further, from the viewpoint of facilitating extrusion molding, a screw having a shape in which the compression ratio of the screw is made small and the supply zone is made long is preferable.

The material of the screw is not particularly limited and can be appropriately selected according to the purpose. In the present invention, for example, a screw whose main body is made of nitride steel, chromium molybdenum steel, or the like and whose surface is coated with metal such as hard chromium or ceramics can be used. Among these, it is preferable to use a screw whose surface is coated with ceramics.
In this case, the polycyano aryl ether does not adhere to the screw or seize during the extrusion. As a result, extrusion molding can be efficiently performed with good moldability while keeping the screw torque low and reducing the load on the motor.

Examples of the ceramics include W
₂ C, metal carbide such as TiC, TiN, ZrN, CrN
And the like, metal carbonitrides such as TiCN, and the like. Among these, W ₂ C, TiN, T
iCN and the like are preferable. These may be used alone or in combination of two or more.

The surface roughness (R _max ) of the screw is not particularly limited, but is preferably 0.2 μm or less. When the surface roughness is within the above range, the screw surface is smooth, and baking of polycyanoaryl ether can be effectively suppressed.

The shape of the die of the extruder is not particularly limited and includes, for example, flat dies such as T dies, fish tail dies, coat hanger dies, dies with screws; straight dies, crosshead dies, offset dies. Examples include circular dies such as dies and inflation dies; or annular dies for pipes, pellet nozzles, and other dies for profiles. Among these, the coat hanger die is preferable. The layout of the die is not particularly limited, and for example, an in-line layout, an offset layout, a crosshead layout, etc. can be appropriately selected.

The extrusion port of the extrusion molding machine (hereinafter referred to as "lip")
Sometimes called. The shape, size, etc. are not particularly limited and can be appropriately selected depending on the intended molded product.

The state of the polycyanoaryl ether supplied to the extruder is not particularly limited, and examples thereof include powder, pellets and flakes. Of these, pellets are preferable.
When it is in the form of pellets, the biting into the screw of the extrusion molding machine is good, and the plasticizing time has little variation, so that sticking to the screw, baking, etc. do not occur.

When polycyanoaryl ether pellets are used, the average weight of the pellets is usually 0.5 to 500 mg, preferably 5 to 200 mg. When the average weight is within the range, the screw is well bitten, and the entire pellet can be melted in a short time.

In the present invention, it is preferable to crystallize the pellets in advance before feeding the pellets to the extruder. In this case, pellets do not become sticky or seized on the screw during extrusion molding.

The supply of the polycyanoaryl ether to the cylinder of the extruder is not particularly limited as long as it can be quantitatively carried out, and may be carried out manually, or a volumetric or gravimetric quantitative feeder, a belt. It may be automatically performed using a mechanical means such as a conveyor or a vibration feeder. Further, the polycyanoaryl ether may be directly supplied to the cylinder, or
The polycyanoaryl ether may be supplied via a hopper provided on the cylinder. When using the hopper, the hopper may be configured to have a function of quantitatively supplying the polycyanoaryl ether contained therein to the cylinder.

The above-mentioned supply is performed so that the supply rate represented by the following equation, supply rate = supply rate / theoretical extrusion rate, is usually 0.2 to 0.6, preferably 0.3 to 0.6. . When the supply rate is within the above range, the fluctuation rate of the extrusion rate can be suppressed to as low as 5% or less. Therefore, even when extrusion-molded into a sheet shape, a film shape, etc., it is possible to obtain an extrusion-molded article having a high commercial value, a uniform wall thickness, and no unevenness. Further, since the filling amount of the polycyanoaryl ether in the cylinder is appropriate, it is possible to prevent the idling of the screw and the increase of the rotating torque, and to provide a stable state without giving an unnecessary load to the motor. Extrusion molding can be performed continuously. On the other hand, if the supply rate is out of the above range, particularly more than 0.6, the supply zone in the cylinder is gradually filled with the polycyanoaryl ether at a high density, and the rotation torque of the screw is increased. is there. Further, if it is less than 0.2, the fluctuation rate of the extrusion amount becomes large, and a high-quality extrusion-molded product with high productivity
It may not be possible to mass-produce.

The supply amount means the amount (kg / hr) of the polycyanoaryl ether supplied to the cylinder.
Means Further, the theoretical extrusion rate means the leakage flow rate (kg / hr) and the pressure flow rate (kg) in the metering zone (measuring section) at the screw tip when the polycyanoaryl ether is densely packed in the cylinder.
/ Hr). The leakage flow rate (Q
_D ) is the following equation Q _D = (1/2) × π ² × D ² × hm × ρ
_m × n × sinΦ × cosΦ, the pressure flow rate (Q _P ).
Is the following equation Q _P = π × D × hm ³ × sin Φ × ρ _m (−
dP / dz) (where D is the screw diameter, z is the axial length of the screw, ρ _m is the density of the polycyanoaryl ether at the time of melting, μ Is the viscosity of the polycyanoaryl ether at the time of melting, n is the rotation speed of the screw, P is the pressure in the cylinder, hm is the depth of the screw groove in the metering zone, and Φ is the deflection angle of the flight. Yes.).

The pressure flow rate (Q _P ) cannot be calculated unless the pressure gradient in the cylinder can be measured. However, in general, the pressure flow rate (Q _P )
The value, the motor so引流amount smaller than the value of (Q _D), the theoretical throughput rate can be considered to be equal to the motor引流amount (Q _D), conveniently from the shape of the screw and the rotational speed Can be calculated. Therefore, in the present invention, by maintaining the supply amount within the range of 20 to 60% of the theoretical extrusion amount, the supply rate is 0.2 to
It can be kept within the range of 0.6.

(3) Extrusion Molding The above-mentioned extrusion molding can be carried out according to a usual extrusion molding method.

The temperature of the extrusion molding, that is, the temperature of the cylinder in the extruder is usually 340 to 40.
It is 0 degreeC, and 340-370 degreeC is preferable. When the temperature is within the above range, the polycyanoaryl ether can be sufficiently melted, and the polycyanoaryl ether is not thermally deteriorated, and a high-quality extruded product that does not cause discoloration or carbide is obtained. be able to. Further, the decrease rate of the molecular weight of the polycyanoaryl ether during extrusion molding can be suppressed to as low as 10% or less, and the transparency of the extrusion molded article and various characteristics such as mechanical strength such as tensile strength and elongation are deteriorated. Can be prevented. on the other hand,
The reduction rate of the molecular weight of the polycyanoaryl ether is 1
If it exceeds 0%, the above-mentioned various properties may be deteriorated and the good characteristics originally possessed by the polycyanoaryl ether may not be utilized.

The shape of the extrusion-molded article obtained by the above-mentioned extrusion molding is not particularly limited and includes, for example, fibrous, monofilament-like, film-like, sheet-like, plate-like, rod-like,
Examples include a profile, a tube, a pipe, a hollow profile, and a thick member.

In the present invention, during extrusion molding, other components such as other polymer components, antioxidants, antistatic agents and lubricants are added to the polycyanoaryl ether within the range not impairing the object of the present invention. Further, additives such as an anti-blocking agent, an ultraviolet absorber, a heat stabilizer, a colorant, a plasticizer and a filler may be appropriately contained.

Examples of the antioxidants include phenolic antioxidants such as butylhydroxyanisole, 2
-A sulfur-based antioxidant such as mercaptobenzothiazole,
Examples include amine antioxidants such as phenyl-α-naphthylamine and phosphoric acid antioxidants such as triphenyl phosphate.

Examples of the antistatic agent include cationic activators, anionic activators, nonionic activators and amphoteric activators.

Examples of the lubricant include hydrocarbon lubricants such as liquid paraffin, chlorinated hydrocarbons and fluorocarbons, fatty acid lubricants such as higher fatty acids and oxyfatty acids, fatty acid amide lubricants such as fatty acid amides and alkylenebisfatty acid amides, Examples thereof include ester lubricants such as esters of lower alcohols / polyhydric alcohols of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, alcohol lubricants, metallic soaps and mixed lubricants.

Examples of the UV absorbers include benzophenone UV absorbers, salicylate UV absorbers, benzotriazole UV absorbers, acrylonitrile UV absorbers, metal complex salts and hindered amine UV absorbers. .

Examples of the colorant include inorganic pigments,
Examples thereof include organic pigments and special pigments. Examples of the inorganic pigment include titanium oxide, red iron oxide, yellow lead, cadmium pigment, ultramarine blue, carbon black and the like. Examples of the organic pigments include insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine pigments, quinacdrine pigments, dioxazine pigments, and dyed lake pigments.

Examples of the plasticizer include phthalic acid ester plasticizers, phosphoric acid ester plasticizers, adipic acid ester plasticizers, sebacic acid ester plasticizers, azelaic acid ester plasticizers, citric acid ester plasticizers, glycolic acid ester plasticizers. Agents, trimellitic acid ester plasticizers, phthalic acid isomer ester plasticizers, ricinoleic acid ester plasticizers, polyester type plasticizers and the like.

Examples of the filler include organic fillers and inorganic fillers. Examples of the organic filler include coconut and coconut shell powder. Examples of the inorganic filler include carbonates such as calcium carbonate, magnesium carbonate and dolomite;
Sulfates such as calcium sulfate and magnesium sulfate; sulfites such as calcium sulfite; silicates such as talc, clay, mica, asbestos, glass fiber, glass beads, calcium silicate, montmorillonite and bentonite; silicon dioxide, alumina, carbonized Ceramics such as silicon and silicon nitride; Viscosity of carion, clay, etc .; MgO, Zn
Examples thereof include metal oxides such as O and TiO ₂ ; and whiskers thereof.

Among these, calcium carbonate, silicon dioxide, alumina, kaolin, bentonite, clay, talc, MgO, ZnO and TiO ₂ are preferable. These may be used alone or in combination of two or more.

The inorganic filler may be in the form of particles, plates or fibers. The particle size of the inorganic filler is preferably 5 μm or less.

The extrusion molded article obtained by the method of the present invention has transparency, heat resistance, chemical resistance, flame retardance, mechanical properties,
It is excellent in various characteristics such as electrical characteristics and can be suitably used in various fields such as electric / electronic equipment field, automobile field, aerospace field and the like.

[0086]

EXAMPLES The present invention will be described more specifically below based on Examples and Comparative Examples. The present invention is not limited to the following embodiments.

(Examples 1 to 6, Comparative Examples 1 to 3) [Formula 2]
Containing 100 mol% of the repeating unit shown in
A twin-screw extruder was used to produce a powdery polycyanoaryl ether having a reduced viscosity [η _sp / c] of 1.2 deciliter / g at 60 ° C. in a solution having a concentration of 0.2 g / deciliter using chlorophenol as a solvent. Cylinder temperature of 350 using a product name PCM-30 manufactured by K.K.
Melt extrusion was performed under the conditions of ℃ and average residence time of 60 seconds, and pelletized. The average weight of the obtained pellets was 20 mg.

Next, the obtained pellets were put into a lip width of 20.
Uniaxial extrusion molding machine with a coat hanger die of 0 mm and lip opening of 0.9 mm (Plastic Engineering Laboratory, cylinder diameter 25 mm, screw length L / diameter D ratio = 28, trade name UT-25-H type) To the cylinder of Table 1, at the pellet feed rate, theoretical extrusion rate, and feed rate to the cylinder shown in Table 1, and under the conditions of the set temperature of the extruder cylinder, the screw surface material, and the screw rotation speed shown in Table 1. Melt extrusion molding was performed to produce a film-shaped extrusion molded article.

The screw used was a full flight type, the compression ratio was 2, the groove depth of the metering zone was 2 mm, and the deflection angle was 17.6 °. Further, theoretical extrusion rates were calculated from the screw rotation speed and screw shape shown in Table 1, and the feed rate was calculated from the calculated values. The density of polyether nitrile when melted is 1.1 g /
It was cm ³ . Furthermore, the rotational torque of the screw, the variation rate of the extrusion rate, and the changes in the reduced viscosity [η _sp / c] before and after the uniaxial extrusion molding were measured under the operating conditions shown in Table 1. The results are shown in Table 1. Screw rotation torque,
The variation rate of the extrusion amount and the reduction rate of the molecular weight of the polycyanoaryl ether before and after the uniaxial extrusion molding were measured as described below.

Under the conditions of Examples 1 to 6 and Comparative Example 1, the screw could be seen from the hopper provided on the cylinder of the single-screw extruder. On the other hand, under the conditions of Comparative Examples 2 and 3, the screw was hidden behind the pellets and could not be seen, and the rotation torque of the screw exceeded 30 A, so the motor tripped and extrusion molding was possible. There wasn't.

<Screw Torque> It was read from the ammeter of the screw motor attached to the uniaxial extruder.

<Variation rate of extrusion rate> The extrusion rate was measured 5 times every 10 minutes for 10 seconds, and the percentage of the standard deviation of the measured values with respect to the average value was taken as the variation rate (%) of the extrusion rate.

[0093] obtains the reduced proportion of reduced viscosity after uniaxial extrusion for reduced viscosity before uniaxial extrusion <reduction rate of the molecular _{weight> [η sp / c] [} η sp / c] (%), which molecular weight The rate of decrease.

[0094]

[Table 1]

[0095]

According to the present invention, polycyanoaryl ether is prevented from decomposing during extrusion molding and its molecular weight is prevented from lowering, while maintaining the screw torque and the variation rate of extrusion amount at a low level. Aryl ether can be extruded and has the above-mentioned various characteristics,
It is possible to provide a method capable of mass-producing an extruded product of a high-quality polycyanoaryl ether that can be suitably used in various fields such as the electronic device field, the automobile field, the aerospace field, and the like with high productivity.

Claims (2)

[Claims] 1. At least 5 repeating units shown in Chemical formula 1
The reduced viscosity [η _sp / c] of a solution containing 0 mol% and having a concentration of 0.2 g / deciliter in a solvent of p-chlorophenol at 60 ° C is 0.5 to 3 deciliter / g.
Is extruded while being supplied to the cylinder of the extruder such that the supply rate represented by the following formula: supply rate = supply rate / theoretical extrusion rate is 0.2 to 0.6. A method for extrusion-molding a polycyanoaryl ether, comprising: Embedded image 2. The screw in the extruder,
The extrusion molding method of polycyanoaryl ether according to claim 1, wherein a screw whose surface is coated with ceramics is used.