Polyether nitrile and method for producing same

Abstract

The present invention addresses the problem of providing a highly crystalline polyether nitrile with which a molded article having high heat resistance and high strength can be obtained with high productivity at a typical mold temperature during injection molding of 200°C or lower. As a solution, provided is a polyether nitrile using 4,4'- biphenol and 2,6-dihalobenzonitrile, having a weight average molecular weight (Mw) of 45,000 or more and a glass transition temperature (Tg) of 190°C or less.

Description

Polyethernitrile and its manufacturing method

[0001] The present invention relates to a polyether nitrile having an improved crystallization rate during molding using a general injection molding machine with a mold temperature of 200°C or less, a method for producing the same, and a resin composition of the polyether nitrile.

[0002] Aromatic ether (co)polymers are useful resins that not only have excellent heat resistance, flame retardancy, chemical resistance, and mechanical strength, but also are thermoplastic and can be molded by heating, making them useful resins that can be used to obtain various molded products such as filaments, films, sheets, tubes, pipes, and round bars by molding methods such as injection molding, extrusion molding, and hot compression molding. Polyethernitriles, which are one type of aromatic ether (co)polymer (e.g., Patent Documents 1 to 4), are resins that have the highest level of heat resistance and excellent mechanical strength among thermoplastic resins. However, these polyethernitriles have a slow crystallization rate, which makes it difficult to sufficiently shorten the molding cycle when producing molded products by hot molding such as injection molding. In particular, a homopolymer of "biphenol-polyethernitrile" having a repeating unit represented by chemical formula (1), obtained using 4,4'-biphenol and 2,6-dihalobenzonitrile, is recognized as a polymer with a glass transition temperature (Tg) exceeding 200°C and high heat resistance and high strength. However, the crystallization rate is slow, and attempts have been made to improve the crystallization rate of polyethernitrile by adding various crystal nucleating agents such as alumina, titanium dioxide, talc, and carbon black, but the results have not been satisfactory (e.g., Patent Documents 5 and 6). Furthermore, polyether nitriles using a small amount of copolymerized component have been disclosed as a method for lowering the melting point while maintaining crystallinity, but in all cases the temperature-decreasing crystallization temperature is lower than that of polymers using a single component, and the crystallization rate is actually reduced (for example, Patent Document 7).

[0003] JP 59-206433, JP 60-147439, JP 61-055120, JP 62-223226, JP 62-240353, JP 01-193354, WO 2021 / 241492

[0004] When molding using a typical injection molding machine with a mold temperature of 200°C or less, resins with a Tg exceeding 200°C inevitably fail to crystallize due to the slow crystal growth rate in a mold below 200°C. Biphenol-polyether nitriles, which typically have a Tg exceeding 200°C, are semi-crystalline polymers and can be crystallized by annealing (heat treatment) above the Tg after molding. However, in practical applications, dimensional changes and warpage during this annealing process can be problematic, necessitating crystallization within the mold during injection molding. Considering the productivity of resin molded products, crystallization must occur within 5 minutes or less in a mold at 200°C or less. However, such a biphenol-polyether nitrile has yet to be discovered. The present invention aims to provide a biphenol-polyether nitrile that overcomes the conventional problems inherent in biphenol-polyether nitriles, which have excellent heat resistance and mechanical strength, and can improve the productivity of molded products.

[0005] As a result of extensive research to solve the above problems, the present inventors have discovered that a polymer having a glass transition temperature (Tg) within a specific range and a molecular weight within a specific range, which is completely unknown among known "biphenol-polyethernitrile" polymers, crystallizes at a practical rate even when the temperature inside the mold during injection molding using a general injection molding machine is 200°C or less, and have completed the present invention. Furthermore, the inventors have discovered that a polymer within the specific molecular weight range has sufficient mechanical strength, and that a desired crystallization rate can be achieved by understanding the relationship between Tg, polymer molecular weight, and molecular weight distribution, as will be described in the Examples below, and by satisfying certain conditions.

[0006] The present invention is as follows: 1. A polyether nitrile having a repeating unit represented by chemical formula (1), which has a weight average molecular weight (Mw) of 45,000 or more in terms of polystyrene as measured by gel permeation chromatography analysis, and a glass transition temperature (Tg) of 190°C or less as measured by a differential scanning calorimetry (DSC) at a temperature increase rate of 10°C per minute. 2. The polyether nitrile according to 1., wherein the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography in terms of polystyrene satisfy the following formula (i): Mw / Mn≧2.16×10 －４ ×Mw-6.64 3. A molding material for the polyethernitrile described in 1.. 4. A molded article of the polyethernitrile described in 1.. 5. A polyethernitrile resin composition containing the polyethernitrile described in 1. and at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). 6. A molded article of the polyethernitrile resin composition described in 5.. 7. A method for producing the polyethernitrile described in 1., which comprises mixing two or more raw material polyethernitriles having repeating units represented by chemical formula (1) and different weight-average molecular weights. 8. A method for producing the polyethernitrile described in 7., in which each of the two or more raw material polyethernitriles having repeating units represented by chemical formula (1) and different weight-average molecular weights is obtained by polycondensation reaction using 4,4'-biphenol having a purity of 99% or more and 2,6-dihalobenzonitrile having a purity of 99% or more. (In the formula, each X independently represents a halogen atom.) 9. A method for producing a polyethernitrile resin composition, comprising mixing the polyethernitrile described in 1. with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). 10. A method for producing the polyethernitrile resin composition described in 9., comprising mixing a raw material polyethernitrile having two or more repeating units represented by chemical formula (1) and different weight-average molecular weights, which when mixed gives the polyethernitrile described in 1., with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). 11. A method for producing a polyethernitrile resin composition, comprising: a raw material polyethernitrile mixing step, wherein the polyethernitrile described in 1. obtained in the raw material polyethernitrile mixing step is obtained by mixing two or more raw material polyethernitriles having repeating units represented by chemical formula (1) and different weight-average molecular weights, to obtain the polyethernitrile described in 1.; and a resin composition component mixing step, wherein the polyethernitrile described in 1. obtained in the raw material polyethernitrile mixing step is mixed with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). A method for producing the polyether nitrile resin composition according to claim 1.

[0007] The polyethernitrile of the present invention has an improved crystallization rate even at low temperatures below 200°C. This allows the production of molded articles with excellent heat resistance and mechanical strength in hot molding, such as injection molding, without the need for post-treatments such as annealing. Furthermore, since the crystallization rate can be improved using only the polyethernitrile resin component, molded articles of polyethernitrile with excellent mechanical strength can be provided without the problem of embrittlement, compared to polyethernitrile resin compositions containing conventionally known crystal nucleating agents. The method for producing the polyethernitrile of the present invention involves mixing two or more raw polyethernitriles with different weight-average molecular weights, which requires a short reaction time and is a rational and simple operation. The polyethernitrile resin composition of the present invention uses the polyethernitrile of the present invention with an improved crystallization rate, allowing molded articles of the polyethernitrile resin composition with excellent heat resistance to be obtained in a short molding cycle. Furthermore, the polyethernitrile resin composition of the present invention requires a short reaction time and can be produced by an industrially simple operation.

[0008] 1 is a graph showing the relationship between the molecular weight distribution (Mw / Mn) and the weight average molecular weight (Mw) of polyether nitrile, in which Mw is in the range of 45,000 or more and 80,000 or less and Mw / Mn is in the range of 1 or more and 21 or less, and the region in the graph where the Tg of the polyether nitrile is 190° C. or less is indicated by a shaded area.

[0009] <Polyethernitrile of the Present Invention> The polyethernitrile of the present invention is a homopolymer having a repeating unit represented by chemical formula (1), which has a weight average molecular weight (Mw) of 45,000 or more in terms of polystyrene as measured by gel permeation chromatography analysis, and a glass transition temperature (Tg) of 190°C or less as measured by a differential scanning calorimetry (DSC) at a temperature increase rate of 10°C per minute. The terminal structure of the polyether nitrile of the present invention is not particularly limited. Both terminals may be hydroxy groups derived from the raw material 4,4'-biphenol, or both terminals may be halogen atoms derived from the raw material 2,6-dihalobenzonitrile compound, or one terminal may be the hydroxy group and the other terminal may be the halogen atom. Furthermore, when a monofunctional halogen chain terminator such as p-phenylphenol, phenol, t-butylphenol, or other monofunctional phenol chain terminator, monohalobenzonitrile, or monohalodiphenyl sulfone is used to control the reaction, or when the hydroxy terminal group is treated with an activated aromatic halide or aliphatic halide such as methyl halide or benzyl halide to convert it to an ether group, the terminal structure may be derived from the compound used in these cases.

[0010] The polyethernitrile of the present invention has a glass transition temperature (Tg) of 190°C or lower. The Tg is preferably 180°C or lower, more preferably 170°C or lower, even more preferably 160°C or lower, and particularly preferably 150°C or lower. The lower the Tg, the faster the crystallization rate of the polyethernitrile, which is preferable, so there is no particular restriction on the lower limit of the range, but a suitable lower limit is determined by the balance between the productivity of the molded article (molding cycle) and the required physical properties such as the heat distortion temperature (HDT). The lower limit of Tg may be 100°C or higher, or even 110°C or higher.

[0011] The polyethernitrile of the present invention has a weight average molecular weight (Mw) of 45,000 or more in terms of polystyrene, as measured by gel permeation chromatography (GPC). A weight average molecular weight (Mw) of less than 45,000 is undesirable because it may result in poor mechanical strength. Furthermore, since moldability becomes difficult, the weight average molecular weight (Mw) is preferably in the range of 45,000 to 1,000,000, more preferably 45,000 to 500,000, and particularly preferably 45,000 to 300,000.

[0012] The polyether nitrile of the present invention preferably has a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of polystyrene, as measured by gel permeation chromatography (GPC), which satisfy the following mathematical formula (i): Mw / Mn≧2.16×10 －４ × Mw - 6.64 This relationship was found by multiple regression analysis of the relationship between the measured values ​​of the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polyethernitrile and Tg, as will be explained in the Examples below. From this, it would be understood by a person skilled in the art of polyethernitriles according to the present invention that polyethernitriles satisfying this relationship have a sufficient crystallization rate. When the relationship of mathematical formula (i) is satisfied, Tg is 190°C or less. Furthermore, when the relationship of mathematical formula (ii) is satisfied, Tg is 180°C or less, which is more preferable, and when the relationship of mathematical formula (iii) is satisfied, Tg is 150°C or less, which is particularly preferable. Mathematical formula (ii): Mw / Mn ≧ 2.16 × 10 －４ × Mw−2.14 Formula (iii): Mw / Mn≧2.16×10 －４ × Mw + 11.34

[0013] <Method for producing the polyethernitrile of the present invention> Examples of methods for producing the polyethernitrile of the present invention include a method (Method 1) in which two or more starting polyethernitriles having different weight-average molecular weights and having a repeating unit represented by the chemical formula (1) are mixed together in advance by separate polycondensation reactions, and a method (Method 2) in which the polyethernitrile is directly obtained by polycondensation reaction. Method 1 is preferred because the polycondensation reaction time required to obtain the starting polyethernitrile used in this method is short and rational, and the polyethernitrile can be produced by a simple operation.

[0014] <Method 1> (Method for Producing Raw Material Polyethernitrile) The raw material polyethernitrile used in Method 1, which is the method for producing a polyethernitrile of the present invention, can be obtained, for example, by subjecting 4,4′-biphenol and a 2,6-dihalobenzonitrile compound represented by general formula (2) to a polycondensation reaction in the presence of a basic compound. (Each X in general formula (2) independently represents a halogen atom.) Specifically, for example, a polyether nitrile having a repeating unit represented by chemical formula (1) can be obtained by polycondensation reaction of 4,4'-biphenol and 2,6-dichlorobenzonitrile as a 2,6-dihalobenzonitrile compound. The reaction formula in this case is shown below. Alternatively, a polycondensation reaction may be carried out using a pre-synthesized alkali metal salt of 4,4'-biphenol and a 2,6-dihalobenzonitrile compound.

[0015] (4,4'-biphenol) 4,4'-biphenol preferably has a purity of 99% by weight or more. In the present invention, purity refers to the purity determined by high-performance liquid chromatography (HPLC) analysis. If the amount of isomers or impurities during the production of 4,4'-biphenol exceeds 1% by weight, the crystallinity of the copolymer may decrease. 4,4'-biphenol can also be used as an alkali metal salt, such as sodium or potassium, obtained by reacting it with an alkali metal compound of an inorganic base, as described below.

[0016] (2,6-Dihalobenzonitrile Compound) The 2,6-dihalobenzonitrile compound is a compound represented by the general formula (2). (In the formula, each X independently represents a halogen atom.) In general formula (2), each X independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, and particularly preferably both Xs are chlorine atoms.

[0017] Specific examples of 2,6-dihalobenzonitrile compounds include 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, and 2,6-dibromobenzonitrile. Among these, at least one selected from 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile is preferably used from the viewpoints of reactivity and economy. Two or more of these compounds can also be used in combination. These 2,6-dihalobenzonitrile compounds preferably have a purity of 99% by weight or more. This purity refers to the purity quantified by high-performance liquid chromatography (HPLC) analysis. If the amount of isomers or impurities exceeds 1% by weight when producing the 2,6-dihalobenzonitrile compound, the crystallinity of the copolymer may decrease.

[0018] The molar ratio of 4,4'-biphenol to the 2,6-dihalobenzonitrile compound can be set arbitrarily depending on the target molecular weight, but is typically in the range of 0.5 to 2.0. For example, when a polymer having an average molecular weight of more than 10 repeating units represented by chemical formula (1) is desired, the molar ratio is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05, and particularly preferably in the range of 0.99 to 1.01. In order to maximize the polymerization rate of the polycondensation reaction, it is preferable to use 4,4'-biphenol and the 2,6-dihalobenzonitrile compound at a molar ratio of substantially 1.00. Conversely, when a polymer having a low molecular weight in which the average number of repeating units represented by chemical formula (1) is 10 or less is desired, the molar ratio is preferably in the range of 0.5 to 0.9 or 1.1 to 2.0.

[0019] (Basic Compound) The basic compound promotes the desalting polycondensation reaction, and may or may not be used as appropriate depending on the target molecular weight. Furthermore, any compound, whether organic or inorganic, may be used as long as it does not affect the quality of the resulting polymer. However, inorganic compounds are preferred, and among these, alkali metal compounds and alkaline earth metal compounds are more preferred, with alkali metal compounds being particularly preferred. Examples of organic bases include tetramethylammonium hydroxide, triethylamine, N,N-diisopropylethylamine, 1,1,3,3-tetramethylguanidine (TMG), N,N-dimethyl-4-aminopyridine (DMAP), 2,6-lutidine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). Cyclo[4.4.0]dec-5-ene (TBD), 1,8-bis(dimethylaminonaphthalene) (DMAN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tert-butylimino-tri(pyrrolidino)phosphorane, tert-butylimino-tris(dimethylamino)phosphorane, 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, tert-octylimino-tris(dimethylamino)phosphorane, phosphazene base P ２ -Et, phosphazene base P ２ -t-Bu, phosphazene base P ３ -t-Bu, phosphazene base P ４ -t-Bu, phosphazene base P ４-t-Oct. Among the inorganic bases, examples of alkali metal compounds include alkali metals such as lithium, rubidium, cesium, potassium, and sodium; alkali metal hydrides such as lithium hydride, rubidium hydride, cesium hydride, potassium hydride, and sodium hydride; alkali metal hydroxides such as lithium hydroxide, rubidium hydroxide, cesium hydroxide, potassium hydroxide, and sodium hydroxide; alkali metal carbonates such as lithium carbonate, rubidium carbonate, cesium carbonate, potassium carbonate, and sodium carbonate; and alkali metal bicarbonates such as lithium bicarbonate, rubidium bicarbonate, cesium bicarbonate, potassium bicarbonate, and sodium bicarbonate. These compounds can be used alone or in combination of two or more. The specific surface area of ​​these alkali metal compounds is 0.3 m or less. ２ By using an alkali metal compound having a specific surface area of ​​0.8 m / g or more, the polycondensation reaction can be carried out with high efficiency. ２ / g or more, and 1.2m ２ / g or more is more preferable. By using an alkali metal compound with a larger specific surface area, the contact opportunity between the catalyst and the reaction raw materials increases, and it becomes possible to carry out the polycondensation reaction with even higher efficiency. ２ When the specific surface area is less than 0.3 m / g, the polycondensation reaction cannot be carried out with sufficiently high efficiency unless the amount of catalyst is increased, but increasing the amount of catalyst is not preferred because it affects the quality of the polycondensate. From the above, as the basic compound, alkali metal carbonates such as lithium carbonate, rubidium carbonate, cesium carbonate, potassium carbonate and sodium carbonate are preferred, and lithium carbonate, potassium carbonate and sodium carbonate are more preferred. In particular, from the viewpoint of availability, alkali metal carbonates with a specific surface area of ​​0.3 m / g are preferred. ２ Potassium carbonate and sodium carbonate having a hydroxyl group of 0.1 to 0.2g or more are preferred.

[0020] The amount of basic compound used in the polycondensation reaction to obtain the starting polyethernitrile is, for example, preferably 2 or more times by mole the alkali metal ion contained in 4,4'-biphenol. However, since a large excess can cause side reactions such as cleavage of ether bonds during polycondensation, a range of 2 to 4 times by mole is more preferable, a range of 2 to 2.4 times by mole is even more preferable, and a range of 2 to 2.2 times by mole is particularly preferable. Furthermore, in order to maximize the polymerization rate of the polycondensation reaction, when 4,4'-biphenol and a 2,6-dihalobenzonitrile compound are used at a molar ratio of substantially 1.00, it is possible to produce polyethernitriles having a molecular weight in which the average number of units of chemical formula (1) ranges from infinity to 1.

[0021] (Reaction Solvent) A reaction solvent can be used in the polycondensation reaction to obtain the raw material polyethernitrile, and it is preferable to use an aprotic solvent as the reaction solvent. Specific examples of aprotic solvents include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzenes (alkoxy groups having 1 to 4 carbon atoms), and trialkoxybenzenes (alkoxy groups having 1 to 4 carbon atoms). Among these solvents, polar organic solvents with high dielectric constants, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, sulfolane, diphenyl sulfone, and dimethyl sulfoxide, are particularly preferred. These solvents can be used alone or in combination of two or more. The amount of aprotic solvent used is not particularly limited as long as it is an amount that uniformly dissolves the raw materials and allows the alkali metal salt to be stirred and dispersed well. The amount should be selected so that the volumetric efficiency of the polycondensation reactor is maximized for the raw materials used and the target polymer. The amount is usually selected in the range of 0.5 to 20 times the total weight of the raw materials and the alkali metal salt.

[0022] (Polycondensation Reaction Method) The polycondensation reaction to obtain the raw material polyethernitrile may be carried out by dividing it into an oligomer formation step (A) and a polymerization step (B), each using a different reaction method, or it may be carried out without dividing the steps. The oligomer formation step (A) is a step in which 4,4'-biphenol and a 2,6-dihalobenzonitrile compound are subjected to a polycondensation reaction in the presence of a basic compound to form an oligomer. The oligomer referred to here is not particularly limited, but a polycondensation reaction product having a polymer reduced viscosity of approximately less than 1 is referred to as an oligomer. The polymerization step (B) is a step in which the oligomer obtained in step (A) is further subjected to a polycondensation reaction to form a polymer. In this case, the polycondensation reaction solution of step (A) can be used as is as the oligomer, or an oligomer isolated by separately carrying out step (A) can also be used.

[0023] When a basic compound is used in the polycondensation reaction to obtain the starting polyethernitrile of the present invention, the reaction involves removing water generated during the salt-forming reaction with 4,4'-biphenol from the system. For example, this can be achieved by reacting the compound in the presence of a solvent that forms an azeotrope with water at a temperature at which the salt-forming reaction proceeds, and then distilling off water from the reaction mixture using a solvent that forms an azeotrope with water. This allows the reaction to be maintained in a substantially anhydrous state. The temperature at which the salt-forming reaction begins varies depending on the starting materials, but is typically around 130°C. For example, when 4,4'-biphenol and 2,6-dichlorobenzonitrile are used as the dihalobenzonitrile compound, potassium carbonate is used as the basic compound, sulfolane (boiling point 285°C) is used as the aprotic solvent, and toluene is used as the solvent that forms an azeotrope with water, a suitable salt-forming reaction temperature is between 130 and 170°C. Specific examples of the solvent that forms an azeotrope with water include aromatic hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole. These can be used alone or in combination of two or more. When using a solvent that forms an azeotrope with water, it is preferable to use 1 to 100 parts by weight of the solvent that forms an azeotrope with water per 100 parts by weight of the aprotic solvent. From the viewpoints of volumetric efficiency and solvent recovery, a range of 1 to 10 parts by weight is more preferable, and a range of 2 to 5 parts by weight is even more preferable.

[0024] When the reaction is continued, it is preferable to maintain the reaction system in a substantially anhydrous state while removing water produced by the reaction. If the water produced is not sufficiently removed, the dihalobenzonitrile compound reacts with water to form a by-product having a phenol skeleton, resulting in the production of only a low molecular weight product. That is, in order to obtain a high molecular weight polyether nitrile, it is preferable to keep the reaction system substantially anhydrous, preferably less than 0.5 wt %.

[0025] (Polycondensation Reaction Conditions) The temperature of the polycondensation reaction to obtain the raw material polyethernitrile is in the range of 140 to 300°C. Within this range, the reaction may be continued at a constant temperature, or the reaction temperature may be increased as the polycondensation reaction progresses. When the polycondensation reaction is carried out in two separate steps, an oligomer formation step (A) and a polymerization step (B), the reaction temperature of the oligomer formation step (A) is preferably in the range of 140 to 200°C, more preferably in the range of 150 to 170°C, and even more preferably in the range of 155 to 165°C. The reaction temperature of the polymerization step (B) is preferably in the range of 190 to 300°C, more preferably in the range of 210 to 270°C, even more preferably in the range of 210 to 240°C, and particularly preferably in the range of 215 to 230°C. For example, when 4,4'-biphenol, 2,6-dichlorobenzonitrile as the dihalobenzonitrile compound, potassium carbonate as the basic compound, sulfolane (boiling point 285°C) as the aprotic solvent, and toluene as the solvent that forms an azeotrope with water, a temperature range of 190 to 280°C is suitable. The pressure for the polycondensation reaction may be atmospheric pressure, or may be higher or lower. The polycondensation reaction is preferably carried out under an inert atmosphere.

[0026] The reaction time for the polycondensation reaction to obtain the raw material polyethernitrile can be set arbitrarily depending on the molar ratio of 4,4'-biphenol to the 2,6-dihalobenzonitrile compound, the amount of the basic compound used, and the target molecular weight, but is usually 3 to 20 hours.

[0027] (Post-reaction treatment) The polycondensation reaction product after the completion of the polycondensation reaction to obtain the raw material polyether nitrile can be used as the raw material polyether nitrile as it is, but it is preferable to carry out post-reaction treatment. The polycondensation reaction product is withdrawn from the reactor, cooled and solidified, and then pulverized to undergo the subsequent washing step, drying step, and step of producing a molding material (pellets, chips), or the polycondensation reaction product withdrawn from the reactor may be directly charged into a washing tank for the washing step, or a solvent to be used in the washing step described below may be poured into the reactor after the completion of the polycondensation reaction, and the polycondensation reaction product may be transferred to the washing step in the form of a slurry or wax.

[0028] The washing step is a step for removing salts, reaction solvents, and the like contained in the polycondensation reaction product obtained by the polycondensation reaction. This washing step is preferably carried out by a known method, using a solvent such as an alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, or water to extract and wash the reaction solvent from the polycondensation reaction product, and then washing and removing salts produced by the desalting reaction in the polycondensation reaction product, preferably with water. Specifically, the polycondensation reaction product in a pulverized, slurry, or waxy state is transferred to a container equipped with a stirrer, and the operations of stirring and washing with a washing solvent and filtration are repeated until the reaction solvent and salt contents are reduced to or below the target levels. As the apparatus, a washing tank and a pressure filter or a centrifuge, as well as a multifunctional filter capable of washing, filtration, and drying in one device, may be used. Specific examples of the extraction and washing solvent for the reaction solvent other than water include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, n-hexyl alcohol, cyclohexanol, n-octyl alcohol, capryl alcohol, etc. Specific examples of ketones include acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone, methyl-t-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, di-n-amyl ketone, diacetyl, acetylacetone, cyclohexanone, benzophenone, etc. Examples of aliphatic hydrocarbons include saturated aliphatic hydrocarbons such as n-hexane, 2-methylheptane, 3-methylheptane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, and cyclohexane; and unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, and cyclohexene.Examples of aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, t-butylbenzene, styrene, and allylbenzene. Among these, methanol, ethanol, acetone, methyl ethyl ketone, xylene, and toluene are preferred, with acetone and methanol being particularly preferred due to ease of operation and ease of distillation recovery of the reaction solvent after washing. Water is preferred for washing salts such as potassium chloride produced in the polycondensation reaction, and acidic water containing low concentrations of oxalic acid or acetic acid may also be used. Conditions for this washing step may include the amount of washing solvent used, the number of washes, and the washing temperature, which may be appropriately selected depending on the amounts of residual reaction solvent and residual alkali metal salts to be removed.

[0029] The drying step is a step of drying the polycondensation reaction product that has been subjected to the above-mentioned washing step. The polycondensation reaction product containing moisture after washing is dried by a known method. Known devices such as an evaporator, a tray oven, or a tumbler can be used as the dryer. The target moisture content is usually 0.5% by weight or less, preferably 0.4% by weight or less, and more preferably 0.3% by weight or less. The conditions for this drying step may be any conditions that allow moisture removal at a temperature below the melting point of the polycondensation reaction product. To minimize contact with air, it is preferable to carry out the drying step under an inert gas (nitrogen, argon, etc.) atmosphere, under an inert gas stream, or under reduced pressure. The dried polycondensation reaction product is basically a powder.

[0030] The raw polyethernitrile used in Method 1, which is the method for producing polyethernitrile of the present invention, may be in the form of a molding material (pellets, chips, etc.) for producing a molded polyethernitrile product. There are no particular limitations on the method for producing such a molding material; however, the powder raw polyethernitrile obtained as described above may be heated and melted and molded into a molding material shape such as pellets or chips. The heating, melting, and molding operations are preferably carried out under an oxygen-shielded condition to prevent oxygen from entering the melting / molding machine, or in an inert atmosphere of an inert gas such as nitrogen or argon. Typically, melt-kneading devices such as single-screw, twin-screw, or multi-screw extruders, Banbury mixers, kneaders, and rollers are used to produce molding materials such as pellets and chips. However, sheets produced using a compression molding machine may also be cut to produce molding materials such as pellets and chips. The industrially preferred process for producing molding materials is as follows: The raw polyethernitrile powder that has been polycondensed, pulverized, washed, and vacuum-dried is directly transferred and stored in a silo sealed with nitrogen gas or the like without being exposed to the outside air. When molding into pellets, chips, or other shapes, the polymer is transferred directly to an extruder through a pipe together with nitrogen gas. The polymer is then melt-kneaded without contact with oxygen (air), and the molten polymer from the die is pelletized by underwater cutting or water-cooled cutting of strands. The conditions for the manufacturing process of this molding material (pellets, chips) are melt processing conditions, where the above operation is carried out at a temperature sufficient to melt the polymer. The upper limit of the melt processing temperature is 500°C or less. Since the raw material polyethernitrile having a repeating unit represented by chemical formula (1) has a melting point of about 350°C, it is preferable to process at a higher temperature, 360°C or more. The upper limit of the temperature is preferably 480°C or less, more preferably 450°C or less, even more preferably 430°C or less, and particularly preferably 400°C or less.

[0031] (Mixing of Raw Polyethernitriles) The polyethernitrile of the present invention can be produced by separately producing two or more raw polyethernitriles having repeating units represented by chemical formula (1) with different weight-average molecular weights by the above-mentioned method, and mixing the respective raw polyethernitriles in appropriate amounts to obtain the polyethernitrile of the present invention. More specifically, taking into account the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of each raw polyethernitrile, appropriate amounts are mixed to obtain the desired Mw and Mn of the polyethernitrile of the present invention. When producing a polyethernitrile having a Tg of 190°C or less, it is preferable to mix the raw polyethernitriles so that the relationship of mathematical formula (i) is satisfied. When producing a polyethernitrile having a Tg of 180°C or less, it is even more preferable to mix the raw polyethernitriles so that the relationship of mathematical formula (ii) is satisfied. When producing a polyethernitrile having a Tg of 150°C or less, it is particularly preferable to mix the raw polyethernitriles so that the relationship of mathematical formula (iii) is satisfied. Furthermore, the polyethernitrile of the present invention can be produced by using the polyethernitrile of the present invention as one of the raw polyethernitriles to be mixed, with the Tg of the polyethernitrile used being lowered or raised to achieve the desired molding cycle. The form of the raw polyethernitrile to be mixed is not particularly limited, and specific examples include the polycondensation reaction product after the polycondensation reaction to obtain the raw polyethernitrile, the washed product of the polycondensation reaction product, powder, and molding material (pellets, chips, etc.). Among these, the form of powder or molding material (pellets, chips, etc.) is preferred, and powder is particularly preferred. The form of two or more raw polyethernitriles to be mixed having different weight-average molecular weights is not particularly limited, and examples include all polycondensation reaction products, all powder, all molding material, polycondensation reaction product and powder, polycondensation reaction product and molding material, and powder and molding material. Among these, all powder, all molding material, or powder and molding material are preferred, and all powder is more preferred.When mixing all components in powder form, when mixing all components in the form of molding material, or when mixing powder and molding material, they may be mixed without melting, or may be mixed by heating and melting. When mixing by heating and melting, the components may be directly subjected to the process of preparing a molding material, which will be described later. When mixing including the form of a polycondensation reaction product or a washed product of the polycondensation reaction product, it is preferable to obtain the polyethernitrile of the present invention by such mixing, and then treat it according to the above-mentioned post-reaction treatment method to remove salts and reaction solvents contained in the polycondensation reaction product, and to remove moisture contained therein. By performing such treatment, a powder of the polyethernitrile of the present invention can be obtained. It is preferable to perform such mixing under oxygen isolation or in an inert atmosphere such as nitrogen, in order to obtain a polyethernitrile with excellent melt fluidity.

[0032] <Method 2> In the method (Method 2) for directly obtaining the polyethernitrile of the present invention by polycondensation reaction, similar to the method for producing the raw material polyethernitrile, the polyethernitrile can be obtained by polycondensation reaction in the presence of 4,4'-biphenol, a 2,6-dihalobenzonitrile compound, and a basic compound. The types of 4,4'-biphenol, 2,6-dihalobenzonitrile compound, and basic compound that can be used in the polycondensation reaction, the type and amount of reaction solvent, the polycondensation reaction method, and the polycondensation reaction conditions are the same as those for the polycondensation reaction of the raw material polyethernitrile described above. The molar ratio of 4,4'-biphenol to the 2,6-dihalobenzonitrile compound is substantially 1.00, and the polycondensation reaction is carried out using at least 1 mole of the basic compound relative to 4,4'-biphenol, in the case of an alkali metal compound, for example, as the alkali metal ion contained therein. The polycondensation reaction time needs to be continued until the reduced viscosity of the polyethernitrile increases as the polycondensation reaction progresses, reaches a maximum, and then begins to decrease, thereby obtaining the polyethernitrile of the present invention. Specifically, the polyether nitrile of the present invention can be obtained by continuing the reaction for a period of 15 to 50 hours, preferably 20 to 50 hours, depending on conditions such as the amount of the basic compound used and the reaction temperature.

[0033] (Post-reaction treatment) After the polycondensation reaction is completed, the polycondensation reaction product is extracted from the reactor, cooled and solidified, and then pulverized to undergo the subsequent washing and drying steps and the step of producing a molding material (pellets, chips). Alternatively, the polycondensation reaction product extracted from the reactor may be directly charged into a washing tank for the washing step, or a solvent to be used in the washing step described below may be injected into the reactor after the polycondensation reaction is completed, and the product may be transferred to the washing step in a slurry or wax state. The washing and drying steps performed on the polycondensation reaction product after the polycondensation reaction are performed in the same manner as the washing and drying steps performed on the polycondensation reaction product after the polycondensation reaction to obtain the raw material polyethernitrile described above.

[0034] (Polyethernitrile Molding Material of the Present Invention) The polyethernitrile of the present invention obtained by the above-described method 1 or 2 can be formed into a molding material (pellets, chips, etc.) for producing a molded article. There are no particular limitations on the method for producing the molding material; however, the polyethernitrile of the present invention obtained as described above may be heated and melted and molded into a molding material shape such as pellets or chips. The heating, melting, and molding operations are preferably carried out under an oxygen-shielded or inert atmosphere such as nitrogen. Typically, a melt-kneading device such as a single-screw, twin-screw, or multi-screw extruder, a Banbury mixer, a kneader, or a roller is used to produce molding materials such as pellets or chips. However, a sheet produced using a compression molding machine may be cut to produce molding materials such as pellets or chips. The industrially preferred process for producing the molding material is as follows: The polyethernitrile powder that has been polycondensed, pulverized, washed, and vacuum-dried is directly transferred and stored in a silo sealed with nitrogen gas or the like without being exposed to the outside air. When molding into pellets, chips, or the like, it is transferred directly through a pipe to an extruder together with nitrogen gas. The polymer is then melt-kneaded without contact with oxygen (air), and the molten polymer from the die is pelletized by underwater cutting or water-cooled cutting of strands. The conditions for the manufacturing process of this molding material (pellets, chips) are melt processing conditions, in which the above operation is carried out at a temperature sufficient to melt the polymer. The upper limit of the melt processing temperature is 500°C or less. Since the polyether nitrile having the repeating unit represented by chemical formula (1) has a melting point of about 350°C, it is preferable to process at a higher temperature of 360°C or more. The upper limit of the temperature is preferably 480°C or less, more preferably 450°C or less, even more preferably 430°C or less, and particularly preferably 400°C or less.

[0035] (Polyethernitrile Resin Composition of the Present Invention) The polyethernitrile of the present invention can be prepared as a polyethernitrile resin composition by mixing at least one selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). The polyethernitrile of the present invention used here is preferably a polyethernitrile obtained by Method 1.

[0036] Specific examples of the thermoplastic resin material (A) contained in the polyethernitrile resin composition include high-density polyethylene, medium-density polyethylene, isotactic polypropylene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, acrylic resin, fluororesin (such as polytetrafluoroethylene), polyester, polycarbonate, polyarylate, aliphatic polyamide, aromatic polyamide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylene sulfide, polyetherimide, polyamideimide, polyesterimide, and modified polyphenylene oxide. Specific examples of the additive (B) contained in the polyethernitrile resin composition include hydrophilic agents, antioxidants, secondary antioxidants, flame retardants, flame retardant aids, plasticizers, lubricants, release agents, antifogging agents, weather stabilizers, light stabilizers, hydrolysis resistance improvers, flow improvers, UV absorbers, antistatic agents, metal deactivators, near-infrared absorbers, and colorants (dyes and pigments). Specific examples of the filler (C) contained in the polyethernitrile resin composition include various metal powders, powders of inorganic acid metal salts (calcium carbonate, zinc borate, calcium borate, zinc stannate, calcium sulfate, barium sulfate, etc.), powders of metal oxides (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.), powders of metal hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (boehmite), etc.), powders of metal sulfides (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.), and ceramic materials such as silver nanowires, carbon fiber, glass fiber, carbon nanotubes, graphene, and silica. These (A) to (C) can be blended in appropriate amounts depending on the intended use, but the total blend amount of (A) to (C) is preferably 90 wt % or less based on the total weight of the polyethernitrile resin composition.

[0037] (Method for producing the polyethernitrile resin composition of the present invention) The method for producing the polyethernitrile resin composition of the present invention is a method for mixing the polyethernitrile of the present invention with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). The polyethernitrile used here is preferably in the form of a powder or a molding material. In such a mixing method, when the polyethernitrile of the present invention produced by Method 1 is used, it is also possible to mix two or more raw material polyethernitriles having different weight-average molecular weights that will form the polyethernitrile of the present invention when mixed with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). In this case, the process for mixing the components preferably includes first performing a "raw material polyethernitrile mixing step" in which two or more raw material polyethernitriles having different weight-average molecular weights and repeating units represented by chemical formula (1) are mixed to obtain the polyethernitrile of the present invention in the same manner as in Method 1, which is the production method for the polyethernitrile of the present invention, and then performing a "resin composition component mixing step" in which the polyethernitrile obtained in the "raw material polyethernitrile mixing step" is mixed with at least one member of the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). When the polyethernitrile of the present invention produced by Method 2 is used, the powder or molding material of the polyethernitrile of the present invention is mixed with at least one member of the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C).

[0038] The polyethernitrile resin composition of the present invention thus obtained can be used to produce a molding material of the polyethernitrile resin composition in the same manner as in the production of the above-mentioned molding material. Since a molding material of the polyethernitrile resin composition having excellent melt fluidity can be obtained, it is preferable that the melt molding in the step of producing the molding material be carried out in an oxygen-shielded environment or in an inert atmosphere.

[0039] The polyethernitrile and polyethernitrile resin composition of the present invention can be used as molding materials by the above-mentioned methods, or can be used to produce molded articles and parts, and have heat resistance, chemical resistance, flame retardancy, and high mechanical properties. For example, they can be used in electrical and electronic applications such as personal computers and semiconductor parts, automotive applications such as gears, bearings, and engine housings, medical devices, and aerospace applications.

[0040] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0041] The analytical methods used in the present invention are as follows. (1) Measurement of Molecular Weight The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained polyethernitrile were measured by diluting a 1% p-chlorophenol solution of the polyethernitrile by 10 times with chloroform, and measuring the solution using the following apparatus and under the following conditions. The molecular weight distribution Mw / Mn was calculated from these values. Apparatus: Gel permeation chromatography: 515 HPLC pump, 717plus automatic injection device, 2487 UV-visible detector (manufactured by Nihon Waters K.K.) Column: 2×PLgel 5μMIXED-D, 7.5×300 mm (Agilent Technologies) Column temperature: 40°C Flow rate: 1.0 mL / min Injection volume: 2.5 μL Detection: UV-visible detector: 254 nm Column calibration: monodisperse polystyrene (EasiCal PS-1 Agilent Technologies) Molecular weight calibration: relative calibration method (polystyrene equivalent) Analysis software: Empower3 (manufactured by Nihon Waters K.K.) (2) Reduced viscosity η of polymer ｒｅｄ Method for measuring reduced viscosity (dL / g): 0.1 g of sample was dissolved in approximately 5 g of parachlorophenol at 180°C, transferred to a 10 mL measuring flask, and diluted to volume at 40°C. The mixture was then adjusted to volume with a 5 mL volumetric pipette and placed in an Ostwald tube (capillary tube 0.75 mm), which was then left to stand in a thermostatic bath at 40.0°C for 15 minutes. The flow time T was measured and the reduced viscosity η was calculated using the following formula. [Calculation formula] ｒｅｄ = {(T / T ０ )-1} / C C: concentration of solution (g / dL) T: flow time of sample solution (seconds) T０ : Flow time of parachlorophenol (seconds) (3) Analysis of thermal properties: Melting point (Tm), glass transition temperature (Tg), heat of crystallization, heat of fusion Using a differential scanning calorimeter (Shimadzu Corporation: DSC-60), thermal properties were measured using pellets and sheets of polyether nitrile obtained in the examples and comparative examples described below, and standard PEEK resin, under the following conditions. The melting point (Tm), glass transition temperature (Tg), heat of recrystallization, and heat of fusion were measured while increasing the temperature by 10°C per minute. <Conditions> Sample: 10 mg Nitrogen flow rate: 50 mL / min Temperature change range: 50 to 370°C Temperature change rate: 10°C / min (4) Measurement of crystallinity The crystallinity of the resin was calculated using the calorific value determined from the DSC measurement in (3) using the following formula. Crystallinity (%) = (heat of fusion - heat of recrystallization) / heat of fusion of perfect crystal × 100 The following values ​​were used for the heat of fusion of perfect crystal: Polyethernitrile of the present invention: 139 J / g, Standard PEEK resin (PEEK450G manufactured by Victrex): 130 J / g The heat of fusion of perfect crystal of the polyethernitrile of the present invention was calculated by the following formula from the crystallinity (22.4%) calculated by X-ray diffraction (XRD) of a sample obtained by melting the resin obtained in Example 6 at 380°C and then holding it at 200°C for 5 minutes to crystallize it, the heat of recrystallization (0.0 J / g) determined by DSC measurement, and the heat of fusion (31.2 J / g). Heat of fusion of perfectly crystalline PEEK (J / g) = (heat of fusion - heat of recrystallization) / (XRD crystallinity) × 100 = (31.2 J / g - 0.0 J / g) / 22.4 × 100 = 139 J / g. The literature value (Polymer Handbook 4th Edition) was used for the heat of fusion of perfectly crystalline PEEK.

[0042] Synthesis Example 1 A four-necked, 3-liter reaction vessel equipped with a mechanical stirrer, a thermometer, a dry nitrogen inlet, and a reflux condenser was charged with 298.45 g (1.735 mol) of 2,6-dichlorobenzonitrile (hereinafter referred to as "DCBN"; purity 99.90 wt % as determined by high-performance liquid chromatography), 323.08 g (1.735 mol) of 4,4'-biphenol (hereinafter referred to as "BP"; purity 99.95 wt % as determined by high-performance liquid chromatography), 251.79 g (1.822 mol; 1.050 times the molar ratio of BP) of anhydrous potassium carbonate, 60 g of toluene, and 1562 g of anhydrous sulfolane. This mixture was heated from room temperature in a nitrogen stream and, while stirring at 250 rpm, heated to 160°C under reflux. At temperatures above 130°C, carbon dioxide was generated from the reaction of potassium carbonate and BP. After 3 hours at 160°C, the oligomerization reaction between DCBN and BP was completed. The cooling water in the reflux condenser was then switched to hot water, and the temperature was raised to 220°C by removing water and toluene from the reflux condenser outlet, and the polycondensation reaction was carried out for 1.5 hours. After the polycondensation reaction, the polycondensation reaction product was removed from the bottom of the reactor and allowed to cool and solidify. The solid product was pulverized in a Waring blender, washed with acetone and distilled water, and dried in a vacuum oven at 120°C for 16 hours to obtain 470 g of powdered raw material polyethernitrile (hereinafter referred to as "raw material resin A") (yield: 95%).

[0043] Synthesis Example 2 A powdery raw material polyethernitrile (hereinafter referred to as "raw material resin B") was obtained in the same manner as in Synthesis Example 1, except that the polycondensation reaction was carried out at a temperature of 220°C for 8.0 hours.

[0044] Synthesis Example 3 A powdery raw material polyethernitrile (hereinafter referred to as "raw material resin C") was obtained in the same manner as in Synthesis Example 1, except that the amount of anhydrous potassium carbonate in Synthesis Example 1 was changed to 237.40 g (1.718 mol: 0.990 times the molar amount of BP) and the polycondensation reaction was carried out for 5 hours.

[0045] Synthesis Example 4 A powdery raw material polyethernitrile (hereinafter referred to as "raw material resin D") was obtained in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, the polycondensation reaction was carried out at a temperature of 220°C for 3.0 hours, and the pulverized product was washed with acetone and 1% oxalic acid water, and then with distilled water.

[0046] Synthesis Example 5 A powdery raw material polyethernitrile (hereinafter referred to as "raw material resin E") was obtained in the same manner as in Synthesis Example 1, except that the amount of anhydrous potassium carbonate in Synthesis Example 1 was changed to 237.42 g (1.718 mol: 0.990 times the molar amount of BP) and the reaction was carried out at 220°C for 1 hour.

[0047] Synthesis Example 6 A powder compound (hereinafter referred to as "Compound A") was obtained in the same manner as in Synthesis Example 1, except that the amount of anhydrous potassium carbonate in Synthesis Example 1 was changed to 143.87 g (1.041 mol: 0.600 times the molar amount of BP), and after reaction at 160°C for 3 hours, the toluene and water were not removed and the reaction was continued at 160°C for 2 hours, and the obtained pulverized product was washed with a 4 wt% aqueous sodium hydroxide solution, hydrochloric acid, and distilled water.

[0048] Synthesis Example 7 A powdery compound (hereinafter referred to as "Compound B") was obtained in the same manner as in Synthesis Example 6, except that in Synthesis Example 6, 149.23 g (0.868 mol) of DCBN and 239.79 g (1.735 mol: 1.000 times by mole relative to BP) of anhydrous potassium carbonate were used, and after the reaction at 160°C for 3 hours, toluene and water were not extracted and the reaction was continued at 160°C for 5 hours.

[0049] The raw material polyether nitriles (raw material resins A to E) obtained in Synthesis Examples 1 to 7 and compounds A and B were analyzed by the above analytical methods to determine the weight average molecular weight (Mw), number average molecular weight (Mn), reduced viscosity η ｒｅｄ The results and the "Mw / Mn" values ​​are shown in Table 1.

[0050]

[0051] Examples 1 to 6, Comparative Examples 1 to 8 The raw material polyethernitriles (raw material resins A to E) obtained in Synthesis Examples 1 to 7 above and Compounds A and B were powder mixed in the raw material types and weight ratios shown in the Raw Material (1) and Raw Material (2) columns in Table 2 below, and melt-kneaded at 380°C under nitrogen under the following conditions, and the resulting strands were pelletized. (Melt-kneading conditions) Apparatus: Circulation kneader [Xplore MC15HT] (manufactured by Xplore Instrument) Temperature / time: 380°C / 5 min. Rotation speed: 100 rpm Screw shape: Conical twin screw Kneading environment: N ２ The weight average molecular weight (Mw), number average molecular weight (Mn), Tm and Tg of the obtained polyether nitrile were measured by the above-mentioned methods. The results are shown in Table 2.

[0052]

[0053] As shown in Table 2, the polyethernitriles of Examples 1 to 6 of the present invention have a Tg of 190°C or less, which is lower than that of the polyethernitriles of Comparative Examples 1 to 8. It was also revealed that the Tg was significantly lower than that of polyethernitriles having similar weight-average molecular weights (Comparative Example 5 vs. Example 5, Comparative Example 7 vs. Example 4), and that the crystallization rate may have been significantly improved. It was also revealed that the polyethernitriles of the present invention maintain a high melting point (Tm) of about 350°C and are highly heat resistant once crystallized.

[0054] Example 7 A polyimide film was placed on a 150 mm x 150 mm x 1 mm stainless steel plate, and a 20 mm wide spacer with a thickness of 0.12 mm, a vertical dimension of 80 mm, and a horizontal dimension of 60 mm was placed thereon. 1 g of the polyethernitrile obtained in Example 1 was filled into the spacer. A polyimide film was then placed on top of the polyimide film, and another 150 mm x 150 mm x 1 mm stainless steel plate was placed on top of the polyimide film (hereinafter, this set is referred to as the "molding mold"). The resulting assembly was then loaded onto the lower heating platen of a press molding machine (Toyo Seiki Mini Test Press MP-2FH, simulating the heating cylinder of an injection molding machine) that had been preheated to 380°C. After loading the "molding mold," the upper heating platen was immediately lowered to apply pressure. The pressure reached 10 MPa within 30 seconds, and the resin was melted at 380°C for 30 seconds. This 380 ° C. "molding mold" was removed from the hot platen and quickly loaded onto the lower hot platen of another press molding machine (Toyo Seiki Mini Test Press MP-2FH: assumed mold for injection molding machine) that had been preheated to 160 ° C. The upper hot platen was immediately lowered and a pressure of 10 MPa was applied, and held for 1 minute. After 1 minute, the "molding mold" was removed from the hot platen and quenched with an attached water-cooled cold press. The spacer with the polyethernitrile sheet sandwiched between the polyimide films was removed from the "molding mold", and a polyethernitrile sheet with a thickness of 0.1 mm, length of 80 mm, and width of 60 mm was obtained. The crystallinity calculated by measuring the heat of recrystallization and heat of fusion of the obtained molded piece using DSC was 26%.

[0055] <Evaluation of Crystallization Rate of Polyethernitrile: Examples 8 to 16, Comparative Examples 9 and 10, Reference Examples 1 to 4> Resin sheets were prepared and the crystallinity was measured in the same manner as in Example 7, except that the resin used, mold temperature, and mold retention time in Example 7 were changed as shown in Table 3 below. The results are shown in Table 3.

[0056]

[0057] As shown in Table 3, in Examples 7 to 16, when a resin of the present invention having a Tg of 190°C or less was used, sufficient crystallization was demonstrated with a holding time of 5 minutes or less, even when the mold temperature during injection molding was 200°C or less. Even when using polyethernitrile obtained by conventional polymerization (Comparative Example 9, Reference Example 1) or a mixture of two or more raw material polyethernitriles with different weight-average molecular weights (Comparative Example 10), it was clear that crystallization was insufficient even with a holding time of 5 minutes at a mold temperature of 200°C or less unless the Tg was 190°C or less. In particular, when the Tg was 150°C or less, it was found that the resin exhibited a crystallization rate equivalent to that of PEEK, which has a Tg of 143°C, at a mold temperature of 200°C or less (Example 7 and Reference Example 2).

[0058] <Evaluation of Mechanical Strength of Polyethernitrile> <Example 17> Test specimens of the following sizes were prepared from the polyethernitrile sheet obtained in Example 7, and the tensile strength and tensile elongation were measured under the following conditions using a universal testing machine AG-50kNXDplus (load cell: 5 kN: manufactured by Shimadzu Corporation). - Test specimen shape: JIS K6251 dumbbell type No. 6 - Test speed: 100 mm / min. Test temperature / humidity: 23°C / 50% RH The results are shown in Table 4.

[0059] Examples 18 and 19, Reference Examples 5 and 6 Using sheets of the resins shown in Table 4 below, the tensile strength and tensile elongation were measured in the same manner as in Example 17. The results are shown in Table 4.

[0060] Comparative Example 11: A resin sheet was prepared using the raw material resin C obtained in Synthesis Example 3 in the same manner as in Example 7, and an attempt was made to prepare a dumbbell to measure the tensile properties using the method described in Example 17. However, the sheet was brittle and cracked, making it impossible to obtain a test piece. Therefore, it was impossible to measure the tensile strength and tensile elongation. The results are shown in Table 4.

[0061]

[0062] Table 4 shows that even when the molecular weight distribution is broadened to lower the Tg, mechanical properties are maintained at a level equivalent to that of PEEK 450G as long as the weight average molecular weight is about 50,000 (45,000 or more). The polyether nitrile of the present invention is extremely useful because it has a fast crystallization rate and can produce molded articles with excellent heat resistance and mechanical strength in a short molding cycle equivalent to that of PEEK.

[0063] <Relationship between Tg and weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)> Using the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and Tg (°C) measured for the polyether nitriles of the Synthesis Examples, Examples, and Comparative Examples listed in Table 5, the relationships between Tg (°C), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were analyzed by multiple regression analysis using Microsoft Excel, and the corrected R ２ The analytical results could be obtained with a high accuracy of 0.995, and it was found that the relationship represented by formula (I) was achieved. The above measured values ​​used in the multiple regression analysis are shown in Table 5, and the results of the multiple regression analysis are shown in Table 6. Formula (I): Tg = 0.000486 × Mw - 2.224 × Mw / Mn + 175.23

[0064]

[0065]

[0066] From the formula (I), it has become clear that the relationship between the molecular weight distribution (Mw / Mn) and the weight average molecular weight (Mw) of polyether nitriles having a Tg of 190°C or less can be expressed by the following formula (i): Mw / Mn≧2.16×10 －４ × Mw-6.64 That is, in the relationship between the molecular weight distribution (Mw / Mn) and the weight average molecular weight (Mw), Mw / Mn = 2.16 × 10 －４It has been revealed that polyether nitriles having a molecular weight distribution (Mw / Mn) and a weight average molecular weight (Mw) that fall in the region above the line: Mw / Mn = 2.16 x 10 - 6.64 give a Tg of 190°C or less. Figure 1 shows a graph of the relationship between molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) in the range of Mw 45,000 or more and 80,000 or less, and Mw / Mn in the range of 1 or more and 21 or less. The molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) of polyether nitriles that fall in the region above the line: Mw / Mn = 2.16 x 10 －４ When the Tg is in the shaded region above "Mw / Mn ≧ 2.16×10", the Tg is 190°C or less. Furthermore, from formula (I), it has become clear that the relationship between the molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) of polyether nitriles having a Tg of 180°C or less can be expressed by formula (ii), and the relationship between the molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) of polyether nitriles having a Tg of 150°C or less can be expressed by formula (iii). Formula (ii): Mw / Mn≧2.16×10 －４ × Mw−2.14 Formula (iii): Mw / Mn≧2.16×10 －４ × Mw + 11.34

[0067] Table 7 shows the Tg, Mw / Mn, calculated values ​​of the right-hand sides of the formulas (i) to (iii), and whether or not the formulas (i) to (iii) are satisfied for the polyether nitriles of Comparative Examples 1 to 8 and Examples 1 to 6. In Table 7, in the columns "Satisfies formula (i)," "Satisfies formula (ii)," and "Satisfies formula (iii)," "◯" means that the formula is satisfied, and "×" means that the formula is not satisfied.

[0068]

[0069] It was revealed that, among the polyethernitriles of the present invention having a Tg of 190°C or less, the polyethernitrile of Example 1 satisfies the relationships of the mathematical formulae (i) to (iii), the polyethernitriles of Examples 2, 3, 4, and 6 satisfies the relationships of the mathematical formulae (i) and (ii), and the polyethernitrile of Example 5 satisfies the relationship of the mathematical formula (i), while the polyethernitriles of Comparative Examples 1 to 8, which had a Tg of more than 190°C, did not satisfy any of the relationships of the mathematical formulae (i) to (iii).

[0070] The above examples are based on biphenol-polyethernitrile, which is a typical polyethernitrile and is said to have a slow crystallization rate. However, those skilled in the art will understand that by applying the method of the present invention to all polyethernitriles, such as 2,7-naphthalene-polyethernitrile, which is said to have a slower crystallization rate, as well as to resorcinol-polyethernitrile and hydroquinone-polyethernitrile, which have a relatively fast crystallization rate, it is possible to control the Tg and produce polyethernitriles with an extremely fast crystallization rate. Furthermore, the application of the technology of the present invention to other polyether resins that are difficult to crystallize will be readily apparent to those skilled in the art and is self-evident from the present invention.

Claims

1. A polyether nitrile having a repeating unit represented by chemical formula (1), which has a weight average molecular weight (Mw) of 45,000 or more in terms of polystyrene as measured by gel permeation chromatography analysis, and a glass transition temperature (Tg) of 190°C or less as measured by a differential scanning calorimetry (DSC) at a temperature increase rate of 10°C per minute.

2. The polyether nitrile according to claim 1, wherein the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography satisfy the following formula (i): Mw / Mn≧2.16×10 －４ ×Mw-6.64 3. A molding material of the polyether nitrile according to claim 1.

4. A molded article of the polyether nitrile according to claim 1.

5. A polyethernitrile resin composition comprising the polyethernitrile according to claim 1 and at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B) and a filler (C).

6. A molded article made from the polyether nitrile resin composition according to claim 5.

7. The method for producing a polyether nitrile according to claim 1, wherein two or more raw material polyether nitriles having repeating units represented by the chemical formula (1) and different weight-average molecular weights are mixed.

8. The method for producing polyether nitriles according to claim 7, wherein each of the two or more raw material polyether nitriles having repeating units represented by chemical formula (1) and having different weight-average molecular weights is obtained by polycondensation reaction of 4,4'-biphenol having a purity of 99% or more and 2,6-dihalobenzonitrile having a purity of 99% or more and represented by general formula (2). (In the formula, each X independently represents a halogen atom.) 9. A method for producing a polyether nitrile resin composition, comprising mixing the polyether nitrile according to claim 1 with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C).

10. A method for producing the polyether nitrile resin composition according to claim 9, comprising mixing a raw material polyether nitrile having two or more repeating units represented by chemical formula (1) with different weight-average molecular weights, which, when mixed, produces the polyether nitrile according to claim 1, with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C).

11. A method for producing the polyethernitrile resin composition according to claim 9, comprising: a raw material polyethernitrile mixing step of obtaining the polyethernitrile according to claim 1 by mixing two or more raw material polyethernitriles having repeating units represented by chemical formula (1) and differing in weight average molecular weight; and a resin composition component mixing step of mixing the polyethernitrile according to claim 1 obtained in the raw material polyethernitrile mixing step with at least one member selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C).