Method of producing polyethernitrile

Abstract

[The technical problem to be solved] The objective of this invention is to provide a method for manufacturing a polyether nitrile with high molecular weight, high fluidity, and excellent heat resistance or mechanical properties. Technical means to solve the problem As a solution to this problem, the present invention provides a method for manufacturing polyether nitrile, which involves manufacturing polyether nitrile by performing a polycondensation reaction of an aromatic dihydroxy compound (I) and a dihalogen benzyl nitrile compound (II), wherein, as the polycondensation proceeds and the polymer reduced viscosity at 40°C in the chlorophenol solution exceeds 1 and reaches a maximum value, the reaction continues until the polymer reduced viscosity decreases.

Description

Technical Field

[0001] The present invention relates to a method for producing a polyether nitrile having a high molecular weight and high fluidity. Prior Art

[0002] Aromatic ether copolymers not only have excellent heat resistance, flame retardancy, chemical resistance, and mechanical strength, but are also thermoplastic and can be melt-molded by heating. Therefore, various molded products such as filaments, films, sheets, tubes, pipes, and round rods can be obtained by molding methods such as injection molding, extrusion molding, and hot compression molding. They are one of the useful resins. (Co)polymers generally involve adding a resin material, heating and melt-kneading it, forming a molding material (resin composition) such as pellets or chips, and then processing it into various molded products. Aromatic ether copolymers are useful as matrix resins for molding materials (resin compositions). Polyether nitrile, one of the aromatic ether copolymers (for example, Patent Documents 1 and 2), has the highest grade of heat resistance among thermoplastic resins and is a resin with excellent mechanical strength. However, the melting point of polyether nitrile is very high, and it needs to be molded at a high temperature close to 400°C. Increasing the molecular weight of the resin is an effective method for improving mechanical properties, but it will further increase the melting temperature and cause problems with poor fluidity. [Prior Art Documents] [Patent Documents]

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. Sho 60-147439 Patent Document 2: Japanese Patent Application Laid-Open No. Sho 61-055120 Summary of the Invention Problems to be Solved by the Invention

[0004] The problem of the present invention is to provide a method for producing a polyether nitrile having a high molecular weight, high fluidity, and excellent high heat resistance or mechanical properties. Means for Solving the Problems

[0005] The present inventors have conducted intensive studies to solve the above problems and as a result, have found that by long-term polycondensation satisfying specific conditions, a polyether nitrile having both a high molecular weight and high fluidity (low viscosity) can be obtained, thereby completing the present invention.

[0006] The present invention is described below. 1. A method for manufacturing polyether nitrile, comprising a polycondensation reaction of an aromatic dihydroxy compound (I) and a dihalogenated benzyl nitrile compound (II) in the presence of an alkaline compound. The reduced viscosity of polyether nitrile increases to more than 1 as the polycondensation reaction proceeds, and continues to react to the region where the reduced viscosity decreases after reaching a maximum value. 2. The method for manufacturing polyether nitrile as described in 1, wherein the aforementioned reduced viscosity increases to more than 1.5 as the polycondensation reaction proceeds, and continues to react to the region where the reduced viscosity decreases after reaching a maximum value. 3. The method for manufacturing polyether nitrile as described in 1, wherein the aforementioned reduced viscosity increases to more than 1.75 as the polycondensation reaction proceeds, and continues to react to the region where the reduced viscosity decreases after reaching a maximum value. 4. The method for manufacturing polyether nitrile as described in 1, wherein the aforementioned reduced viscosity increases to more than 2.0 as the polycondensation reaction proceeds, and continues to react to the region where the reduced viscosity decreases after reaching a maximum value. 5. The method for manufacturing polyether nitrile as described in 1, wherein the aforementioned aromatic dihydroxy compound (I) is a compound represented by the following general formula (1), and the aforementioned dihalogen benzyl nitrile compound (II) is a compound represented by the following general formula (2); [HO-R-OH (1)] (In the formula, R represents the divalent base shown in general formula (1a) or general formula (1b) below) (In the formula, R1 independently represents a straight-chain or branched-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 or 6 carbon atoms, or a phenyl group; m independently represents an integer from 0 to 4; n represents 0 or 1; p and q independently represent 0, 1, or 2; and * represents the bond position.) (In the formula, R1 and m are defined as in general formula (1a), Y represents oxygen atom, sulfur atom, sulfonyl, carbonyl, alkylene with 1 to 15 carbon atoms, fluorinated alkylene with 2 to 15 carbon atoms, cycloalkylene with 5 to 15 carbon atoms, phenylmethylene, phenylethylene, phenylene or fumonisin, Z represents oxygen atom, sulfur atom or no bridging, Ar independently represents aryl with 6 to 8 carbon atoms, and * represents the bonding position.) (In the formula, X independently represents a halogen atom, and r represents an integer of 1 to 4). 6. The method for producing a polyether nitrile according to 1., wherein R in the compound represented by the general formula (1) is the following general formula (1a') or the following general formula (1a"), (In the formula, R1, m and * are the same as defined in the general formula (1a)). 7. The method for producing a polyether nitrile according to 1. or 5., wherein in the polycondensation reaction, the molar ratio of the aromatic dihydroxy compound (I) to the dihalogenobenzonitrile compound (II) is in the range of (I):(II)=1:0.99 to 1:1.005. 8. The method for producing a polyether nitrile according to 1., wherein in the polycondensation reaction, the basic compound is an alkali metal compound, and it is used in a range of 2 to 4 molar times relative to the aromatic dihydroxy compound (I) in terms of the alkali metal ions contained in the alkali metal compound. 9. The method for producing a polyether nitrile according to 1., wherein the weight average molecular weight (Mw) of the obtained polyether nitrile is in the range of 40,000 to 1,000,000, and the ratio (Mw / Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) is in the range of 2.7 to 4.0. Effect of the Invention

[0007] According to the production method of the present invention, a polyether nitrile having both high molecular weight and high fluidity (low viscosity) and excellent heat resistance or mechanical properties can be obtained, so it is extremely useful. Brief Explanation of the Drawings

[0008] Figure 1 is a chart showing the change in reduced viscosity converted from the polycondensation time and stirring torque in Comparative Example 1. Figure 2 is a chart showing the change in reduced viscosity converted from the polycondensation time and stirring torque in Example 1. Figure 3 is a chart showing the change in reduced viscosity converted from the polycondensation time and stirring torque in Example 2. Embodiment

[0009] This invention relates to a method for manufacturing polyether nitrile, which involves a polycondensation reaction of an aromatic dihydroxy compound (I) and a dihalogenated benzyl nitrile compound (II) in the presence of an alkaline compound. The reduced viscosity of the polyether nitrile increases to more than 1 as the polycondensation reaction proceeds, and continues to increase after reaching a maximum value until a region of reduced reduced viscosity is reached. From the viewpoint of increasing the weight average molecular weight of the obtained polyether nitrile, the reduced viscosity preferably increases to more than 1.5, and continues to increase after reaching a maximum value until a region of reduced reduced viscosity is reached; more preferably, it increases to more than 1.75, and continues to increase after reaching a maximum value until a region of reduced reduced viscosity is reached; particularly preferably, it increases to more than 2.0, and continues to increase after reaching a maximum value until a region of reduced reduced viscosity is reached. Furthermore, the "reduced viscosity" of this invention is a value obtained in the following manner. Dissolve 0.1g of sample in 5g of p-chlorophenol at 180℃, transfer to a 10mL volumetric flask at 40℃ and add to the mark. Make up to volume with a 5mL whole pipette and place into an Ostwald tube (0.75mm capillary). Let it stand in a constant temperature bath at 40.0℃ for 15 minutes and measure the flow time T. The value calculated by the following formula is taken as the "reduced viscosity ηred". [Formula] Reduced viscosity ηred = {(T / T0) - 1} / C. C: Solution concentration (g / dL). T: The time (in seconds) for the sample solution to flow down. T0: Flow time of p-chlorophenol (seconds). When implementing the manufacturing method of the present invention, as a method for determining the progress of the polycondensation reaction, a portion of the polycondensation reaction solution is sampled, and the reduced viscosity of the polymer obtained after washing is determined in the manner described above, thereby making a determination. Furthermore, as detailed in the embodiments described later, the "reduced viscosity" of the present invention has been confirmed to be correlated with the stirring torque of the polycondensation reaction liquid in the polycondensation process. That is, when implementing the manufacturing method of the present invention, a method can be used to determine the increase or decrease of the reduced viscosity of the polymer by measuring the stirring torque of the polycondensation reaction liquid. For example, samples of the polycondensation reaction liquid in the experiment can be taken at various desired time points in advance. The stirring torque value measured by a torque meter at each sampling time point and the reduced viscosity of the polymer obtained after washing each sample can be measured. The relationship between the stirring torque and the reduced viscosity of the polymer can be determined from the measured values, and the reduced viscosity in the polycondensation can be calculated and determined from the stirring torque. As confirmed in the following embodiments, the reduced viscosity and the measured stirring torque of the present invention can be expressed by the formula "Reduced viscosity (dl / g) = A × Stirring torque (Nm) + B". In this formula, A and B are values ​​determined based on the reactor, stirring blades, motor, and reaction conditions used.

[0010] When a compound of general formula (1), which is an aromatic dihydroxy compound (I), and a compound of general formula (2), which is a dihalogen benzyl nitrile compound (II), undergo a polycondensation reaction in the presence of an alkaline compound, a polyether nitrile having repeating units as shown in the following general formula (3) is obtained. The reaction formula is shown below. (In the formula, R, X, and r are defined in the same way as in general formulas (1) to (3).) Alternatively, a pre-synthesized aromatic dihydroxy compound (I) can be used as an alkali metal salt dihalogen benzyl nitrile compound (II) to carry out the polycondensation reaction. In the manufacture of polyether nitrile, the polycondensation reaction can be divided into an oligomer formation step (A) and a polymerization step (B), and the reaction methods can be changed for each step. Alternatively, it can be carried out without any specific steps. The oligomer formation step (A) described above is a step in which an aromatic dihydroxy compound (I) and a dihalogenated benzyl nitrile compound (II) undergo a polycondensation reaction in the presence of an alkaline compound to form an oligomer. Here, there is no particular limitation on the oligomer, but generally speaking, a polycondensation product with a polymer reduced viscosity of less than 1 is referred to as an oligomer. The polymer formation step (B) described above is a step in which the oligomers obtained in step (A) undergo a further polycondensation reaction to form a polymer. At this time, the oligomers can be directly obtained from the polycondensation reaction solution of step (A), or they can be oligomers that have undergone step (A) and been isolated separately. In polycondensation reactions, the removal of water generated during the desalination reaction is included. This can be achieved by, for example, by conducting the reaction at a temperature at which the desalination reaction will occur in the presence of a solvent that forms an azeotrope with water, and by distilling off the water from the reaction mixture using the solvent that forms the azeotrope with water. This maintains the reaction in a substantially anhydrous state. While the starting temperature of the desalination reaction varies depending on the raw materials, it is typically around 130°C. For example, when using 4,4'-biphenol as an aromatic dihydroxy compound (I), 2,6-dichlorobenzyl nitrile as a dihalogenated benzyl nitrile compound (II), potassium carbonate, cyclobutane (boiling point 285°C) as an aprotic solvent, and toluene as a solvent that forms an azeotrope with water, the preferred reaction temperature is 130 to 170°C. Furthermore, during continuous reaction, it is preferable to maintain a substantially anhydrous state in the reaction system while removing the water generated in the reaction. If the removal of the generated water is insufficient, the water will react with the dihalogenated benzyl nitrile compound (II) to generate a phenolic skeleton byproduct, resulting only in low molecular weight products. That is, in order to obtain high molecular weight polyether nitrile, it is preferable that the reaction system is substantially anhydrous, preferably less than 0.5% by weight. Polycondensation reactions can be carried out in an inert gas environment, such as in a nitrogen environment or at atmospheric pressure, but higher or lower pressures can also be used. In the manufacturing method of the present invention, the reduced viscosity of polyether nitrile increases to more than 1 as the polycondensation reaction proceeds, and continues to react to the region where the reduced viscosity decreases after reaching a maximum value.

[0011] <Aromatic Dihydroxy Compounds (I)> The aromatic dihydroxy compound (I) of the present invention includes all aromatic compounds having two hydroxyl groups, wherein, preferably, is a compound represented by the following general formula (1). [HO-R-OH (1)] (In the formula, R represents the divalent base shown in general formula (1a) or general formula (1b) below) (In the formula, R1 independently represents a straight-chain or branched-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 or 6 carbon atoms, or a phenyl group; m independently represents an integer from 0 to 4; n represents 0 or 1; p and q independently represent 0, 1, or 2; and * represents the bond position.) (In the formula, R1 and m are defined in the same way as in general formula (1a), Y represents oxygen atom, sulfur atom, sulfonyl, carbonyl, alkylene with 1 to 15 carbon atoms, fluorinated alkylene with 2 to 15 carbon atoms, cycloalkylene with 5 to 15 carbon atoms, phenylmethylene, phenylethylene, phenylene or fumonisin, Z represents oxygen atom, sulfur atom or no bridging, Ar independently represents aryl with 6 to 8 carbon atoms, and * represents the bonding position.)

[0012] In general formula (1a), R1 independently represents a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group, preferably a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group, more preferably a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, or a phenyl group, and especially preferably an alkyl group having 1 carbon atom, i.e., a methyl group. In general formula (1a), m represents an integer from 0 to 4, preferably an integer of 0, 1 or 2, more preferably 0 or 1, and especially preferably 0. In general formula (1a), n represents 0 or 1, preferably 1. In general formula (1a), p and q independently represent 0, 1 or 2, preferably 0 or 1, and especially 0. When n is 1 and p and q are 0, the above general formula (1a) is expressed as general formula (1a'). (In the formula, R1, m, and * are defined in the same way as in general formula (1a).) In formula (1a'), the position of the OH bond with formula (1) relative to the direct bonding position of the two benzene rings is preferably ortho or para, and particularly preferably para. When m is 1 or 2, the position of the R1 bond relative to the direct bonding position of the two benzene rings is preferably meta. The preferred states of R1 and m are the same as in formula (1a). The above general formula (1a) when n, p and q are 0 is represented by the following general formula (1a”). (In the formula, R1, m, and * are defined in the same way as in general formula (1a).) In general formula (1a”), the position of the OH bond in general formula (1) relative to the position of the other bond is preferably para or meta, and especially para. The preferred states of R1 and m are the same as in general formula (1a). In general formula (1a), the preferred form is general formula (1a') when n is 1 and p and q are 0; or the state of general formula (1a”) when n, p and q are 0.

[0013] The definitions of R1 and m in general formula (1b) are the same as those in general formula (1a), and the better state is also the same. In general formula (1b), Y represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group with 1 to 15 carbon atoms, a fluorinated alkylene group with 2 to 15 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a phenylmethylene group, a phenylethyl group, a phenyl group, or a cycloalkylene group. The aforementioned cycloalkylene groups with 5 to 15 carbon atoms may contain alkyl groups as branched chains. Specifically, examples of cycloalkylene groups include: cyclopentylene (5 carbon atoms), cyclohexylene (6 carbon atoms), 3-methylcyclohexylene (7 carbon atoms), 4-methylcyclohexylene (7 carbon atoms), 3,3,5-trimethylcyclohexylene (9 carbon atoms), cycloheptylene (7 carbon atoms), and cyclododecylene (12 carbon atoms). In general formula (1b), Y is preferably sulfonyl, carbonyl, alkylene with 1 to 6 carbon atoms, fluorinated alkylene with 2 to 6 carbon atoms, cycloalkylene with 5 to 12 carbon atoms, phenylmethylene, phenylethylene, phenylene, or genistein; more preferably sulfonyl, methyl, alkylene with 1 to 3 carbon atoms, fluorinated alkylene with 2 or 3 carbon atoms, cycloalkylene with 6 to 12 carbon atoms, phenylmethylene, or genistein; even more preferably alkylene with 3 carbon atoms (i.e., propylene), fluorinated alkylene with 3 carbon atoms (i.e., fluorinated propylene), cycloalkylene with 6 to 12 carbon atoms, or genistein; particularly preferably 2,2'-isopropylene, 2,2'-hexafluoroisopropylene, cyclohexylene, 3,3,5-trimethylcyclohexylene, cyclododecylene, or genistein. In general formula (1b), Z represents an oxygen atom, a sulfur atom, or a non-bridging atom, preferably an oxygen atom or a non-bridging atom, and more preferably a non-bridging atom. In general formula (1b), Ar independently represents aryl groups with 6 to 8 carbon atoms, preferably aryl groups with 6 carbon atoms. In general formula (1), R is preferably a divalent base as shown in general formula (1a), more preferably a divalent base as shown in general formula (1a') or general formula (1a”), and especially preferably a divalent base as shown in general formula (1a').

[0014] Specifically, the aromatic dihydroxy compound (I) of this invention can be exemplified by, for example: hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4'-biphenol, 3,3'-biphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,1'-bi-2-naphthol, 2,2'-bi-1-naphthol, 1,3-bis[1-methyl-1-(4-hydroxyphenyl)ethyl-1-benzene, 1,4 ... [1-Methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,3-(4-hydroxybenzylbenzene), 1,4-(4-hydroxybenzylbenzene), 1,3-bis(4-hydroxyphenoxy)benzene, 1,4-bis(4-hydroxyphenoxy)benzene, 1,4-bis(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, 4,4'-isopropylidene biphenyl (Bis-A), 2,2-bis(4-hydroxyphenyl)-1,1 1,3,3,3-Hexafluoropropane, 4,4'-Dihydroxydiphenyl ketone, 4,4'-Dihydroxydiphenyl ether, 4,4'-Dihydroxydiphenyl ether, bis(4-hydroxyphenyl)methane, 9,9-bis(4-hydroxyphenyl)furan, 9,9-bis(3-phenyl-4-hydroxyphenyl)furan, 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)furan, 9,9-bis(4-hydroxy-3-methylphenyl)furan, 9,9-bis(4- Hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3-cyclohexylphenyl) bis(4,4'-isopropylidene bis(2-phenylphenol), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, etc. Among them, hydroquinone, resorcinol, and 4,4'-biphenol are preferred, and 4,4'-biphenol is particularly preferred.

[0015] <Dihalogenated benzyl nitrile compound (II)> The dihalogenated benzyl nitrile compound (II) of the present invention includes all benzyl nitrile compounds having two halogen groups, wherein the compounds shown in the following general formula (2) are preferred. (In the formula, X represents a halogen atom independently, and r represents an integer from 1 to 4.) In the above general formula (2), X represents a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, and most preferably a chlorine atom. In the above general formula (2), r represents an integer from 1 to 4, preferably 1 or 2, and especially 1. When r is 1, it is more preferably a structural state in which the halogen atom is bonded to the two adjacent positions of the cyano group.

[0016] Specifically, examples of the dihalogenated benzyl nitrile compounds (II) of this invention include, for example: 2,6-difluorobenzyl nitrile, 2,5-difluorobenzyl nitrile, 2,4-difluorobenzyl nitrile, 2,6-dichlorobenzyl nitrile, 2,5-dichlorobenzyl nitrile, 2,4-dichlorobenzyl nitrile, 2,6-dibromobenzyl nitrile, 2,5-dibromobenzyl nitrile, 2,4-dibromobenzyl nitrile, 2,6-dinitrobenzyl nitrile, 2,5-dinitrobenzyl nitrile, 2,4-dinitrobenzyl nitrile, and 1,4-dichloro-2,5-dicyanobenzene. Reactive derivatives of these compounds are also possible. From the viewpoints of reactivity and economy, 2,6-difluorobenzyl nitrile and 2,6-dichlorobenzyl nitrile are particularly suitable. These compounds can also be used in combination of two or more. When listing the aforementioned reactive derivatives using the structure derived from 2,6-dihalogen benzyl nitrile as an example, compounds that can react with aromatic dihydroxy compounds can be cited as shown in the following general formula. This means that these are compounds derived from the reaction of two 2,6-dihalogen benzyl nitriles or 2,6-dihalogen benzyl nitriles with aromatic dihydroxy compounds. (In the formula, the R system is defined the same as in general formula (1), and the X system is defined the same as in general formula (2).)

[0017] <Raw Material Usage> In the manufacturing method of the present invention, the aromatic dihydroxy compound (I) is preferably used in a molar ratio of 0.99 to 1.005 relative to the dihalogenated benzyl nitrile compound (II), more preferably in a molar ratio of 0.995 to 1.005, even more preferably in a molar ratio of 0.998 to 1.002, and most preferably in a molar ratio of 0.999 to 1.001. To maximize the polymerization rate in step (B) above, it is preferable to use the aromatic dihydroxy compound (I) and the dihalogenated benzyl nitrile compound (II) in a molar ratio of substantially 1.000. Aromatic dihydroxy compound (I) and dihalogenated benzyl nitrile compound (II) may be used in combination with only one compound or in combination with two or more compounds. When two or more compounds are used, the molar ratio of the total amount of each compound in aromatic dihydroxy compound (I) and dihalogenated benzyl nitrile compound (II) is used in the manner described above.

[0018] <Alkaline compounds> The basic compound can be any compound, whether organic or inorganic, as long as it promotes the desalting polymerization and condensation reaction without affecting the quality. It is preferably an inorganic compound, and more preferably an alkali metal compound or an alkaline earth metal compound, and especially preferably an alkali metal compound. 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-dimethylpyridine, 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 (TBD), 1,8-bis(dimethylaminonaphthalene) (DMAN), 1,4-diazabicyclo[2.2.2]octane (DABCO), and tert-butylimino-tris(pyrrolidyl)phosphine. Alkane (tert-butylimino-tri(pyrrolidino)phosphorane), tert-butylimino-tri(dimethylamino)phosphorane, 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, tert-octylimino-tri(dimethylamino)phosphorane, phosphonazine base P2-Et, phosphonazine base P2-t-Bu, phosphonazine base P3-t-Bu, phosphonazine base P4-t-Bu, phosphonazine base P4-t-Oct. Among inorganic alkalis, 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. One or more of these compounds may be used. By using alkali metal compounds with a specific surface area of ​​0.3 m² / g or higher, desalting polymerization condensation reactions can be carried out with high efficiency. The specific surface area of ​​the alkali metal compound catalyst is preferably 0.8 m² / g or higher, and more preferably 1.2 m² / g or higher. Using an alkali metal compound catalyst with a larger specific surface area further increases the contact opportunities between the catalyst and the reactants, thus enabling desalting polymerization condensation reactions to proceed with even higher efficiency. When the specific surface area is less than 0.3 m² / g, the desalting polymerization condensation reaction cannot be carried out with sufficiently high efficiency without increasing the amount of catalyst; however, increasing the amount of catalyst will affect the quality of the polycondensate, which is undesirable. Based on the above, the alkaline compound in the manufacturing method of the present invention is preferably an alkali metal carbonate such as lithium carbonate, rubidium carbonate, cesium carbonate, potassium carbonate, and sodium carbonate, more preferably lithium carbonate, potassium carbonate, and sodium carbonate, and especially from the viewpoint of availability, potassium carbonate and sodium carbonate with a specific surface area of ​​0.3 m2 / g or more are preferred. In the manufacturing method of the present invention, the amount of alkaline compound used, for example, when it is an alkali metal compound, is generally preferably more than 2 moles relative to the aromatic dihydroxy compound (I), based on the alkali metal ions contained therein. However, if too much is used, side reactions such as the cleavage of the generated ether bonds may occur during the polycondensation. Therefore, it is more preferably used in the range of 2 to 4 moles, more preferably in the range of 2 to 2.4 moles, and especially preferably in the range of 2 to 2.2 moles.

[0019] Solvent The manufacturing method of the present invention may use a reaction solvent, preferably an aprotic solvent. Specifically, examples of aprotic solvents include: N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, cyclobutane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfoxide, diethyl sulfoxide, diisopropyl sulfoxide, diphenyl sulfoxide, diphenyl ether, diphenyl ketone, dialkoxybenzene (alkoxy carbon number 1 to 4), and trialkoxybenzene (alkoxy carbon number 1 to 4). Among these solvents, polar organic solvents with high dielectric properties, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, cyclobutane, diphenyl sulfoxide, and dimethyl sulfoxide, are particularly suitable. One type can be used, or two or more types can be used in combination. Regarding the amount of aprotic solvent used, there are no particular restrictions, except that it should be sufficient to uniformly dissolve the raw materials and ensure good dispersion of the alkali metal salt. The amount chosen should maximize the volumetric efficiency of the polymerization reactor relative to the raw materials and the intended polymer system. Typically, this is selected within the range of 0.5 to 20 times the total weight of the raw materials and the alkali metal salt. Specifically, solvents that form azeotropes with water include: benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, and dichlorobenzene. Aromatic hydrocarbons such as alkanes, tetrahydrofurans, anisole, and phenetole. One or more of these may be used. 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, relative to 100 parts by weight of an aprotic solvent. From the viewpoint of volumetric efficiency or solvent recovery, it is even more preferable to use 1 to 10 parts by weight, and even more preferable to use 2 to 5 parts by weight.

[0020] <Reaction Temperature> The reaction temperature in the polycondensation reaction is between 140 and 300°C. Within this range, the reaction can be continued at a fixed temperature, or the temperature can be increased as the polycondensation reaction proceeds. When the polycondensation reaction is carried out by dividing the steps into an "oligomer formation step (A)" and a "polymerization step (B)", 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 polymerization step (B) is preferably in the range of 200 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 most preferably in the range of 215 to 230°C. For example, when using 4,4'-biphenol as an aromatic dihydroxy compound (I) and 2,6-dichlorobenzyl nitrile as a dihalogenated benzyl nitrile compound (II), and using potassium carbonate, cyclobutane (boiling point 285°C) as an aprotic solvent, and toluene as a solvent that forms an azeotrope with water, the preferred temperature range is 190 to 280°C.

[0021] The reaction time of the polycondensation reaction in this invention is such that as the polycondensation proceeds, the reduced viscosity of the polyether nitrile increases to more than 1, and after reaching a maximum value, the reaction continues until the reduced viscosity decreases, and the reaction can continue even after it begins to decrease. The reaction time varies depending on the reaction conditions or the raw materials used, and cannot be generalized, but it is usually 3 to 20 hours. When performing a polycondensation reaction by dividing the process into an oligomer formation step (A) and a polymerization step (B), the reaction time of step (A) is preferably continued until almost no carbon dioxide or water is generated, but there is no particular limitation. It is typically 1 to 6 hours, preferably 2 to 4 hours. The same applies to step (B), where the reduced viscosity of the polyether nitrile increases to over 1 and continues to react after reaching a maximum value until the reduced viscosity decreases, and can continue to react even after it begins to decrease. Specifically, the reaction time varies depending on the reaction conditions or the raw materials used, so it cannot be generalized. However, it can be 2 to 12 hours from the time when the reduced viscosity of polyether nitrile reaches 1, preferably 2 to 10 hours, and even more preferably 2 to 9 hours.

[0022] (Post-reaction processing) After the polycondensation reaction is completed, the polycondensation reactants can be taken out of the reactor, cooled and solidified, then crushed, and then proceeded to the subsequent washing, drying, and molding material (granules, flakes) manufacturing steps. Alternatively, the material taken out of the reactor can be directly put into the washing tank of the washing step, or the solvent used in the washing step can be injected into the reactor after the polycondensation reaction is completed, and then transferred to the washing step in slurry or wax state.

[0023] The washing step is a process to remove salts or reaction solvents contained in the polycondensation product obtained by the polycondensation reaction. The washing step can be performed using known methods with solvents such as alcohols, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, and water to extract and wash the reaction solvent in the polycondensation reactants. Then, preferably, the salts generated by the desalting reaction in the polycondensation reactants are washed and removed with water. In terms of specific operation, the pulverized, slurry, or waxy polycondensation reactants can be transferred to a container equipped with a stirrer, and the stirring, washing, and filtering operations can be repeated with a washing solvent until the reaction solvent or salt content is below the target level. In terms of equipment, in addition to using a washing tank and a pressure filter or centrifuge, a multi-functional filter device that can perform washing, filtering and drying in one unit can also be used. Specific examples of extraction and washing solvents other than water, used as reaction solvents, include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, dibutanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol, n-hexanol, cyclohexanol, n-octanol, and octanol. Examples of ketones include acetone, butanone, methyl n-acetone, diethyl ketone, 2-hexanone, 3-hexanone, methyl tert-butanone, di-n-acetone, diisoacetone, diisobutyl ketone, di-n-pentanone, 2,3-butanedione (diacetyl), acetylacetone, cyclohexanone, and diphenyl ketone. Examples of aliphatic hydrocarbon systems include: 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, cyclohexane, and other saturated aliphatic hydrocarbons; and 1-hexene, 1-heptene, 1-octene, cyclohexene, and other unsaturated hydrocarbons. Examples of aromatic hydrocarbon systems include: benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butadiene, tert-butadiene, styrene, allylbenzene, etc. Among these, methanol, ethanol, acetone, butanone, xylene, and toluene are preferred. In terms of operability or ease of distillation recovery of the reaction solvent after washing, acetone or methanol is particularly preferred. For the washing of alkali metal salts such as potassium chloride generated by desalination polymerization reaction, water is preferred, but acidic water containing low concentrations of oxalic acid or acetic acid can also be used. The conditions for this cleaning step are simply to select the appropriate amount of cleaning solvent, number of cleaning cycles, and cleaning temperature in accordance with the amount of residual reaction solvent and residual alkali metal salts to be removed.

[0024] The drying step is a step of drying the polycondensation reactant obtained from the washing step described above. The washed and moisture-containing polymerization-condensation reaction product is dried using known methods. Known devices such as evaporators, plate ovens, and drum dryers can be used for this purpose. The target moisture content is typically below 0.5% by weight, preferably below 0.4% by weight, and even more preferably below 0.3% by weight. The drying step can be performed at a temperature below the melting point of the polymerization condensation reactants to remove moisture. Preferably, it is carried out under reduced pressure in an inert gas environment (nitrogen, argon, etc.) or under an inert gas stream, in a manner that minimizes contact with air.

[0025] The weight-average molecular weight (Mw) of the polyether nitrile manufactured by the method of the present invention will vary depending on the application and is not particularly limited. It can be from 40,000 to 1,000,000, preferably from 50,000 to 500,000, and even more preferably from 60,000 to 300,000. When the molecular weight of the obtained polymer is less than 40,000, the mechanical strength is poor; if it is above 1,000,000, it becomes difficult to mold, and therefore is undesirable. The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw / Mn, is in the range of 2.7 to 4.0, preferably in the range of 2.8 to 3.5, more preferably in the range of 2.9 to 3.5, and particularly preferably in the range of 3.0 to 3.5.

[0026] The polycondensation reactant dried by the above drying steps is essentially a powder. Therefore, this powder can be used to manufacture molding materials (granules, flakes, etc.) for the purpose of producing molded articles. There are no particular limitations on the method of heating and melting the polyether nitrile powder to manufacture molding materials, but it is preferable to carry out the process under oxygen-blocking conditions or inactive gas environments such as nitrogen. Typically, when manufacturing shaped materials such as granules or flakes, single-shaft, dual-shaft, or multi-shaft extruders, Banbury mixers, kneaders, rolling mills, and other melt mixing devices are used. However, compression molding machines, as used in the following examples, can also be used to produce sheets, which are then cut to manufacture shaped materials such as granules or flakes. The preferred industrial process for manufacturing molding materials is described below. Polyether nitrile powder, after polymerization condensation, pulverization, washing, and vacuum drying, is directly transferred to a sealed storage tower or similar facility, sealed with nitrogen, and stored without exposure to external gases. When forming into granules or flakes, it is directly piped to an extruder along with nitrogen. Then, the molten polymer from the die is melt-blended without contact with oxygen (air) and granulated by underwater cutting or water-cooling the filaments. Regarding the manufacturing conditions of the molding material (granules, flakes), the melt processing conditions are to perform the above operations at a temperature that sufficiently melts the polymer. The upper limit of the temperature for melt processing is 500°C or lower. Since the polyether nitrile powder obtained using the biphenol in the example has a melting point of 364°C, it is suitable to be processed at a temperature higher than its melting point, above 380°C. The upper limit of the processing temperature is preferably below 480°C, more preferably below 450°C, even more preferably below 430°C, and most preferably below 400°C.

[0027] A polyether nitrile resin composition can also be formed by mixing "the powder or molding material of polyether nitrile obtained by the manufacturing method of the present invention" and "at least one of the group consisting of thermoplastic resin material (A), additive (B) and filler (C)". When manufacturing polyether nitrile resin compositions, the steps can be the same as those used in manufacturing the molding materials described above. The mixing of the components can be performed using the following methods: 1) pre-mixing polyether nitrile powder or pre-formed polyether nitrile molding materials and other components (A to C) above, and then transferring the mixture to an extruder; 2) pre-mixing polyether nitrile powder or pre-formed polyether nitrile molding materials and other components (A to C) above into molding materials with different compositions, mixing the molding materials in a predetermined amount at the desired content ratio, and then transferring the mixture to an extruder; 3) directly adding polyether nitrile powder or pre-formed polyether nitrile molding materials and other components (A to C) above to an extruder, etc. These methods are preferably performed in a non-reactive gas environment.

[0028] The thermoplastic resin materials (A) contained in the aforementioned polyether nitrile resin composition can specifically be exemplified by: high-density polyethylene, medium-density polyethylene, isotactic polypropylene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, acrylic resin, fluoropolymer (polytetrafluoroethylene, etc.), polyester, polycarbonate, polyarylate, aliphatic polyamide, aromatic polyamide, polyurethane, polyetherurethane, polyetherketone, polyetheretherketone, polyphenylene sulfide, polyetherimide, polyamideimide, polyesterimide, and modified polyphenylene ether. The additives (B) contained in the aforementioned polyether nitrile resin composition can specifically include, for example: hydrophilic agents, antioxidants, secondary antioxidants, flame retardants, flame retardant auxiliaries, plasticizers, lubricants, release agents, anti-turbidity agents, weather stabilizers, light stabilizers, hydrolysis resistance improvers, flowability improvers, ultraviolet absorbers, antistatic agents, metal inactivators, near-infrared absorbers, and colorants (dyes, pigments). The fillers (C) contained in the aforementioned polyether nitrile resin composition can be specifically exemplified by: various metal powders, inorganic acid metal salts (calcium carbonate, zinc borate, calcium borate, zinc stannate, calcium sulfate, barium sulfate, etc.) powders, metal oxides (magnesium oxide, iron oxide, titanium oxide, zinc oxide, aluminum oxide, etc.) powders, metal hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate boehmite, etc.) powders, metal sulfides (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.) powders, silver nanowires, carbon fibers, glass fibers, carbon nanotubes, graphene, silicon dioxide and other ceramic materials. The appropriate amount of (A) to (C) can be prepared according to the intended use. In order to obtain a polyether nitrile resin composition molding material with excellent melt flowability by melt molding the polyether nitrile resin composition of the present invention under oxygen-blocked or inactive gas environment, the amount of these (A) to (C) is preferably set to 90% by weight or less relative to the total weight of the polyether nitrile resin composition.

[0029] The polyether nitrile obtained by the method of the present invention can be used as a molding material for molding by the above method, or for manufacturing molded articles or parts obtained by using the material, and has heat resistance, chemical resistance, flame retardancy, and high mechanical properties. For example, it can be used in electronic and electrical applications such as personal computers or semiconductor parts, automotive applications such as gears or bearings, and engine housings, or applications in medical devices and aerospace fields. (Example)

[0030] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples. The analytical method of this invention is described below. <Analytical Methods> (1) Method for determining reduced viscosity ηred (dL / g) As described above, dissolve 0.1 g of the sample in approximately 5 g of p-chlorophenol at 180°C, transfer to a 10 mL volumetric flask, and add to the mark at 40°C. Dilute to volume using a 5 mL pipette and place into an Oswald tube (0.75 mm capillary). Incubate the Oswald tube in a 40.0°C constant temperature bath for 15 minutes and measure the flow time T. Calculate the flow time using the following formula. [Equation] Reduced viscosity ηred = {(T / T0)-1} / C. C: Solution concentration (g / dL). T: The time (in seconds) for the sample solution to flow down. T0: Flow time of p-chlorophenol (seconds). (2) Methods for determining the reduced viscosity of polymers in polycondensation Beforehand, samples of the polycondensation reaction solution were taken at various desired time points during the experiment. The stirring torque value measured by a torque meter and the reduced viscosity of the polymer obtained after washing each sample were measured at each sampling time point. The relationship between the stirring torque and the reduced viscosity of the polymer were determined from the measured values, and the reduced viscosity in the polycondensation was calculated and determined from the stirring torque. Reduced viscosity (dl / g) = A × stirring torque (Nm) + B. A and B are values ​​determined based on the reactor, stirring blades, motor, and reaction conditions used. (3) Thermal properties: melting point, glass transition temperature (Tg) The thermal properties of the sample were determined using a differential scanning calorimeter (Shimadzu Corporation: DSC-60) under the following conditions. Conditions: Sample size approximately 10 mg, nitrogen flow rate 50 mL / min, temperature range 50℃ to 450℃, temperature change rate 10℃ / min. (4) Determination of molecular weight The molecular weight of the polymer was determined by diluting a 1% p-chlorophenol solution of the polymer 10 times with chloroform, and then measuring the molecular weight of the solution using the following apparatus and conditions. Apparatus: Gel permeation chromatography: 515 HPLC pump, 717plus auto-injection device, 2487 UV-Vis detector (manufactured by WATERS Corporation, Japan). Column: 2×PLgel5μMIXED-D, 7.5×300mm (Agilent Technologies). Column temperature: 40℃. Flow rate: 1.0 mL / min. Injection volume: 2.5 μL. Detection: Ultraviolet-visible light detector: 254nm. Column calibration: Monodisperse polystyrene (EasiCal PS-1 Agilent Technologies). Molecular weight correction: relative comparison correction method (polystyrene conversion). Parsing software: Empower3 (manufactured by WATERS Co., Ltd., Japan).

[0031] <Comparative Example 1> In a 3-liter reactor equipped with a four-necked mechanical stirrer with a torque meter, a thermometer, a dry nitrogen inlet, and a reflux condenser, 298.45 g (1.735 moles) of 2,6-dichlorobenzyl nitrile (hereinafter referred to as "DCBN"), 323.08 g (1.735 moles) of 4,4'-biphenyl (hereinafter referred to as "BP"), 251.79 g (1.822 moles) of anhydrous potassium carbonate, 60 g of toluene, and 1562 g of anhydrous cyclobutane were added. The mixture was heated from room temperature under a nitrogen stream, stirred at 250 rpm, and refluxed until the temperature reached 160°C. Above 130°C, carbon dioxide was produced due to the reaction of potassium carbonate and biphenyl. After 3 hours at 160°C, the oligomerization reaction of "DCBN" and "BP" was completed. Then, the cooling water in the reflux condenser was switched to warm water, and water and toluene were removed from the outlet, thereby raising the temperature to 220°C and carrying out polycondensation. 1.5 hours after the temperature was raised to 220°C and the reduced viscosity calculated from the stirring torque reached 1, the reaction was terminated when the reduced viscosity calculated from the stirring torque reached 2.0. The polycondensation reactant was removed from the bottom of the reactor and allowed to cool and solidify. Furthermore, the relationship between the stirring torque and the reducing viscosity of the polymer during the polycondensation under the aforementioned equipment and conditions is known in advance, and is expressed in the following formula in the experiment. Reduced viscosity (dl / g) = 6.87 × stirring torque (Nm) + 0.684. Using this formula, the reduced viscosity of the polymer is estimated from the torque meter reading during the polycondensation, and the reaction is stopped and the product is removed at the time point when the desired value is displayed. The time from the point when the reduced viscosity, calculated from the stirring torque of the reaction, reaches 1, and the change in the reduced viscosity, calculated from the stirring torque, are shown in Figure 1. After the solid product was pulverized using a Waring blender, it was washed several times with acetone and distilled water and dried in a vacuum oven at 120°C for 16 hours to obtain 470g of polyether nitrile powder (yield 95%). The reaction temperature was increased to 220℃, and after 1.5 hours, the measured reduced viscosity of the resulting polymer powder was 2.0. Furthermore, the obtained polymer powder has a number average molecular weight (Mn) of 28,200, a weight average molecular weight (Mw) of 71,100, a Mw / Mn ratio of 2.52, a melting point of 364℃, and a glass transition temperature (Tg) of 215℃. The data on polymerization condensation time, molecular weight of the resulting polymer, and reduced viscosity of the polymer in Comparative Example 1 are summarized in Table 1 below.

[0032] <Example 1> In the above "Comparative Example 1", after the reaction temperature was raised to 220°C, 1.5 hours after the reduced viscosity calculated from the stirring torque reached 1, the reaction was not terminated at the time point when the reduced viscosity calculated from the stirring torque reached 2.0, but the reaction continued directly at 220°C. As shown in Figure 2, the peak of the reduced viscosity calculated from the stirring torque was 2.8, and then decreased to a reduced viscosity value of 2.3. Three hours after the reduced viscosity calculated from the stirring torque reached 1, the reaction solution was sampled. The reaction was then terminated when the reduced viscosity value reached 1.8 (five hours later), and the polycondensation product was collected. Subsequently, post-processing was performed in the same manner as in "Comparative Example 1" described above. The time when the reduced viscosity, calculated from the stirring torque of the reaction, reaches 1 is set as 0 hours, and the change in reduced viscosity calculated from the stirring torque is shown in Figure 2. Three hours after the reaction temperature was increased to 220°C, the reduced viscosity was 2.2. After a further 5 hours of reaction, the measured reduced viscosity of the polymer (i.e., the polymer powder) was 1.9. The number average molecular weight (Mn) of the obtained polymer powder was 24,200, the weight average molecular weight (Mw) was 73,400, and the Mw / Mn ratio was 3.03. The melting point is 364℃, and the glass transition temperature (Tg) is 215℃. The data on the polymerization condensation time, molecular weight of the resulting polymer, and polymer reduced viscosity of Example 1 are summarized in Table 1 below.

[0033] <Example 2> In the above "Example 1", the time point at which the reduced viscosity, calculated by the stirring torque of the reaction, reaches 1 is set as 0 hours. This 0-hour time point continues until 8 hours. Otherwise, the reaction is carried out in the same manner. The time when the reduced viscosity, calculated from the stirring torque of the reaction, reaches 1 is set as the time of 0 hours, and the change in reduced viscosity calculated from the stirring torque is shown in Figure 3. After raising the reaction temperature to 220℃ and continuing the reaction for 8 hours, the measured reduced viscosity of the resulting polymer powder was 1.55. The number average molecular weight (Mn) of the obtained polymer powder was 22,200, the weight average molecular weight (Mw) was 72,900, and the Mw / Mn ratio was 3.28. The melting point is 364℃, and the glass transition temperature (Tg) is 215℃. The data on the polymerization condensation time, molecular weight of the resulting polymer, and polymer reduced viscosity of Example 2 are summarized in Table 1 below.

[0034] [Table 1]

[0035] As shown in Figures 2 and 3, Examples 1 and 2 are examples where heating was continued until the polymer reduced viscosity exceeded 1 and reached a maximum value before decreasing, representing specific examples of the manufacturing method of the present invention. Comparative Example 1 is an example where, although the polymer reduced viscosity exceeded 1, heating was stopped before the polymer reduced viscosity reached a maximum value. As shown in Table 1, compared to Comparative Example 1, the polymers obtained by the manufacturing method of the present invention in Examples 1 and 2 have lower reduced viscosity but higher weight average molecular weight. Therefore, it can be seen that the manufacturing method of the present invention is a method for obtaining polyether nitrile with high molecular weight and high flowability.

Claims

1. A method for manufacturing polyether nitrile, comprising a polycondensation reaction of an aromatic dihydroxy compound (I) and a dihalogenated benzyl nitrile compound (II) in the presence of an alkaline compound, wherein, The reduced viscosity of polyether nitrile increases to more than 1.5 as the polycondensation reaction proceeds, and after reaching a maximum value, it continues to react until the region where the reduced viscosity decreases.

2. The method for manufacturing polyether nitrile as described in claim 1, wherein, The aforementioned reduced viscosity increases to over 1.75 as the polymerization condensation reaction proceeds, and after reaching a maximum value, it continues to react in the region where the reduced viscosity decreases.

3. The method for manufacturing polyether nitrile as described in claim 1, wherein, The aforementioned reduced viscosity increases to over 2.0 as the polymerization condensation reaction proceeds, and after reaching a maximum value, it continues to react in the region where the reduced viscosity decreases.

4. The method for manufacturing polyether nitrile as described in claim 1, wherein, The aforementioned aromatic dihydroxy compound (I) is the compound shown in the following general formula (1), and the aforementioned dihalogen benzyl nitrile compound (II) is the compound shown in the following general formula (2), wherein R represents a divalent group shown in the following general formula (1a) or the following general formula (1b); wherein R1 independently represents a straight-chain or branched-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 or 6 carbon atoms, or a phenyl group, m independently represents an integer from 0 to 4, n represents 0 or 1, p and q independently represent 0, 1 or 2, and * represents the bond position; In the formula, R1 and m are defined as in general formula (1a), Y represents oxygen atom, sulfur atom, sulfonyl, carbonyl, alkylene with 1 to 15 carbon atoms, fluorinated alkylene with 2 to 15 carbon atoms, cycloalkylene with 5 to 15 carbon atoms, phenylmethylene, phenylethylene, phenylene or fumonisin, Z represents oxygen atom, sulfur atom or no bridging, Ar independently represents aryl with 6 to 8 carbon atoms, and * represents the bonding position; In the formula, X independently represents halogen atom, and r represents an integer from 1 to 4.

5. The method for manufacturing polyether nitrile as described in claim 1, wherein, In the compound represented by the aforementioned general formula (1), R is the following general formula (1a') or the following general formula (1a”), wherein R1, m and * are defined in the same way as in general formula (1a).

6. A method for manufacturing polyethernitrile as described in claim 1 or 4, wherein, In the aforementioned polycondensation reaction, the molar ratio of the aromatic dihydroxy compound (I) and the dihalogenated benzyl nitrile compound (II) is in the range of (I):(II) = 1:0.99 to 1:1.

005.

7. The method for manufacturing polyether nitrile as described in claim 1, wherein, In the aforementioned polycondensation reaction, the basic compound is an alkali metal compound, and is used in the range of 2 to 4 moles relative to the aromatic dihydroxy compound (I), based on the alkali metal ions contained in the alkali metal compound.

8. The method for manufacturing polyether nitrile as described in claim 1, wherein, The weight average molecular weight (Mw) of the aforementioned polyether nitrile is in the range of 40,000 to 1,000,000, and the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw) (Mw / Mn) is in the range of 2.7 to 4.0.

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