Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used

Definitions

• the present invention relates to a production method in which melt fluidity is stable when repeatedly producing polyethernitrile.
• Aromatic ether copolymers are not only excellent in heat resistance, flame retardancy, chemical resistance and mechanical strength, but are also thermoplastic and can be melt-molded by heating. It is one of the useful resins that can be formed into various molded articles such as filaments, films, sheets, tubes, pipes and round bars by molding methods such as hot compression molding.
• the (co)polymer is generally made into a molding material (resin composition) such as pellets and chips after heating, melting and kneading by adding a resin material, and processing this into various molded products.
• Ether-based copolymers are useful as base resins for molding materials (resin compositions).
• Polyethernitrile (for example, Patent Documents 1 and 2), which is one of aromatic ether-based copolymers, has the highest level of heat resistance among thermoplastic resins and is a resin excellent in mechanical strength.
• a polymer powder is obtained by washing and drying the polyethernitrile obtained by the polycondensation reaction. This powder is used as a molding material such as pellets and chips so that it can be easily processed. There is a demand for the ability to stably produce molded articles having good qualities such as heat resistance and mechanical properties using polyethernitrile resins and molding materials thereof.
• An object of the present invention is to provide a method for producing a polyethernitrile with stable melt fluidity, which suppresses fluctuations and deterioration of melt fluidity during molding when polyethernitrile is repeatedly produced.
• the present inventors found that when repeatedly producing polyethernitrile, a large amount of the polymer obtained by the polycondensation reaction remains in the reactor, and the residue is included.
• the inventors have found that the melt fluidity of the resulting polyethernitrile during molding fluctuates and deteriorates by conducting a new polycondensation reaction, and the present invention has been completed on the basis of this finding.
• the present invention is as follows. 1.
• the aromatic dihydroxy compound (I) is a compound represented by the following general formula (1)
• the dihalobenzonitrile compound (II) is a compound represented by the following general formula (2). .
• R represents a divalent group represented by the following general formula (1a) or the following general formula (1b).
• each R 1 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms or a phenyl group
• each m independently represents represents an integer of 0 to 4
• n represents 0 or 1
• p and q each independently represent 0, 1 or 2
• Y is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, and 2 to 15 fluorine-containing alkylidene groups, cycloalkylidene groups having 5 to 15 carbon atoms, phenylmethylidene groups, phenylethylidene groups, phenylene
• Ar each independently represents an aryl group having 6 to 8 carbon atoms, and * represents each bonding position.
• each X independently represents a halogen atom, and r represents an integer of 1 to 4.
• R in the compound represented by the general formula (1) is the following general formula (1a′) or the following general formula (1a′′), and r in the compound represented by the general formula (2) is 1. , 2. The method for producing a polyethernitrile described in 2. above. (Wherein, R 1 , m and * are the same as defined in general formula (1a).) (Wherein, R 1 , m and * are the same as defined in general formula (1a).) 4. 3.
• the compound represented by the general formula (1) is at least one selected from hydroquinone, resorcin and 4,4'-biphenol;
• the basic compound (III) is an alkali metal compound;
• the residual amount of the polymer after removing the polymer remaining in the reactor in the step 3 is 5000 ppm with respect to the theoretical yield of the polymer obtained from the reaction raw materials supplied to the reactor when performing a new polycondensation reaction. 1.
• the manufacturing method described in . 7. 1. Further comprising a step (step 4) of washing the polymer taken out from the polycondensation reactor in step 2 of the preceding paragraph.
• the reduced viscosity ⁇ red of the resulting polyethernitrile is in the range of 1 to 5;
• the polycondensation reactor is a batch reactor.
• the present invention relates to a method for producing a polyethernitrile by subjecting an aromatic dihydroxy compound (I) and a dihalobenzonitrile compound (II) to a polycondensation reaction in the presence of a basic compound (III). , aromatic dihydroxy compound (I), dihalobenzonitrile compound (II), and basic compound (III), a step of supplying a reaction raw material and a reaction solvent to carry out a polycondensation reaction (step 1); A step of removing the polymer obtained by the reaction from the polycondensation reactor (step 2), removing the polymer remaining in the polycondensation reactor, and supplying a new reaction raw material and a reaction solvent to the polycondensation reactor. and a step (step 3) of performing a new polycondensation reaction.
• the step (step 1) of supplying a reaction raw material and a reaction solvent to a polycondensation reactor (hereinafter sometimes simply referred to as a reactor) to perform a polycondensation reaction is the aromatic dihydroxy compound (I ), a dihalobenzonitrile compound (II) and a basic compound (III) as reaction raw materials and a reaction solvent, a conventionally known polycondensation reaction of polyethernitrile can be applied.
• the method of supplying the reaction raw materials and the reaction solvent to the reactor is not particularly limited.
• the reaction raw materials and the reaction solvent may be supplied to the reactor in order, or may be supplied to the reactor at the same time. .
• the step of removing the polymer obtained by the polycondensation reaction from the polycondensation reactor can be performed by a conventionally known method, which will be described in detail later.
• a method of extracting a polymer obtained by a polycondensation reaction (hereinafter sometimes simply referred to as a polymer) by extracting the condensation reaction product as it is, or a method of adding a solvent to the polycondensation reaction product in the reactor and extracting it as a solution.
• a method for extracting the polymer can be mentioned.
• step (step 3) of removing the polymer remaining in the polycondensation reactor and supplying a new reaction solvent and reaction raw materials to the polycondensation reactor to perform a new polycondensation reaction As a method for removing the polymer remaining in the polymerization apparatus, which will be described later in detail, for example, a method of using a good solvent for the polymer or water to wash the polymer remaining in the polymerization apparatus can be mentioned.
• the method of supplying a new reaction solvent and reaction raw materials to the polycondensation reactor and performing a new polycondensation reaction is the same method as in step 1 in the polycondensation reactor after removing the residual polymer described above. A polycondensation reaction is carried out.
• Step 1 The step (step 1) of supplying a reaction raw material and a reaction solvent to a polycondensation reactor to carry out a polycondensation reaction in the present invention will be described below.
• the aromatic dihydroxy compound (I) in the present invention includes all aromatic compounds having two hydroxyl groups, but among them, compounds represented by the following general formula (1) are preferred.
• R represents a divalent group represented by the following general formula (1a) or the following general formula (1b).
• each R 1 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms or a phenyl group
• each m independently represents represents an integer of 0 to 4
• n represents 0 or 1
• p and q each independently represent 0, 1 or 2
• Y is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, and 2 to 15 fluorine-containing
• Each R 1 in the general formula (1a) independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group;
• a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group is preferred, and a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group is more preferred, and an alkyl group having 1 carbon atom, that is, a methyl group is particularly preferred.
• Each m in the general formula (1a) independently represents an integer of 0 to 4, preferably an integer of 0 or 1 to 2, more preferably 0 or 1, and particularly preferably 0.
• n in the general formula (1a) represents 0 or 1, preferably 1.
• p and q in general formula (1a) each independently represent 0, 1 or 2, preferably 0 or 1, particularly preferably 0;
• the above general formula (1a) when n is 1 and p and q are 0 is represented by the following general formula (1a').
• R 1 , m and * are the same as defined in general formula (1a).
• the position bonding to OH of general formula (1) in general formula (1a′) is preferably ortho- or para-position relative to the direct bonding positions of the two benzene rings, particularly para-position. preferable.
• the bonding position of R 1 is preferably meta to the direct bonding position of the two benzene rings.
• Preferred aspects of R 1 and m are the same as in general formula (1a).
• General formula (1a) when n, p and q are 0 is represented by the following general formula (1a'').
• R 1 , m and * are the same as defined in general formula (1a).
• the position of bonding to OH of general formula (1) in general formula (1a′′) is preferably para-position or meta-position with respect to the other bonding position, particularly preferably para-position.
• R 1 and Preferred aspects of m are the same as those of general formula (1a).
• R 1 and m in general formula (1b) are the same as defined in general formula (1a), and preferred embodiments are also the same.
• Y in the general formula (1b) is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, and an alkylidene group having 5 to 15 carbon atoms. It represents a cycloalkylidene group, a phenylmethylidene group, a phenylethylidene group, a phenylene group or a fluorenylidene group, and the cycloalkylidene group having 5 to 15 carbon atoms may contain an alkyl group as a branched chain.
• cycloalkylidene group examples include a cyclopentylidene group (having 5 carbon atoms), a cyclohexylidene group (having 6 carbon atoms), a 3-methylcyclohexylidene group (having 7 carbon atoms), 4 -methylcyclohexylidene group (7 carbon atoms), 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), cycloheptylidene group (7 carbon atoms), cyclododecanylidene group (carbon number of atoms 12) and the like.
• Y in the general formula (1b) is a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 6 carbon atoms, a fluorine-containing alkylidene group having 2 to 6 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, a phenylmethyl A ridene group, a phenylethylidene group, a phenylene group or a fluorenylidene group is preferable, and a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 3 carbon atoms, a fluorine-containing alkylidene group having 2 or 3 carbon atoms, and a A cycloalkylidene group, a phenylmethylidene group or a fluorenylidene group is more preferable, and an alkylidene group having 3 carbon atoms, namely a propylid
• Z in the general formula (1b) represents an oxygen atom, a sulfur atom, or no cross-linking, preferably an oxygen atom or no cross-linking, more preferably no cross-linking.
• Each Ar in the general formula (1b) independently represents an aryl group having 6 to 8 carbon atoms, more preferably an aryl group having 6 carbon atoms.
• R in the general formula (1) is preferably a divalent group represented by the general formula (1a), a divalent group represented by the general formula (1a′) or a general formula (1a′′) A divalent group represented by the general formula (1a′) is particularly preferable.
• aromatic dihydroxy compound (I) in the present invention examples include 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]benzene, 1,4-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,3-(4-hydroxybenzoylbenzene), 1,4-(4-hydroxybenzoylbenzene), 1,3- bis(4-hydroxyphenoxy)benzene, 1,4-bis(4-hydroxyphenoxy)benzene, 1,4-bis(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, 1,
• At least one of these compounds may be used, and only one of them may be used, or two or more of them may be used in combination.
• at least one selected from hydroquinone, resorcin and 4,4'-biphenol is preferred, hydroquinone, resorcin and 4,4'-biphenol are more preferred, and 4,4'-biphenol is particularly preferred.
• the dihalobenzonitrile compound (II) in the present invention includes all nitrile compounds having two halogen groups, but among them, compounds represented by the following general formula (2) are preferred.
• each X independently represents a halogen atom, and r represents an integer of 1 to 4.
• X in the general formula (2) each independently represents a halogen atom, preferably each independently a chlorine atom, a bromine atom or an iodine atom, each independently a chlorine atom or a bromine atom More preferably, both are chlorine atoms.
• r in the general formula (2) represents an integer of 1 to 4, preferably 1 or 2, more preferably 1. When r is 1, a structural aspect in which halogen atoms are bonded to both ortho-positions of the cyano group is preferred.
• dihalobenzonitrile compound (II) in the present invention examples include 2,6-difluorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichloro benzonitrile, 2,5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-dibromobenzonitrile, 2,5-dibromobenzonitrile, 2,4-dibromobenzonitrile, 2,6-dinitrobenzonitrile , 2,5-dinitrobenzonitrile, 2,4-dinitrobenzonitrile, 1,4-dichloro-2,5-dicyanobenzene.
• these reactive derivatives may be used.
• 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoint of reactivity and economy.
• the compound represented by the general formula (2) these compounds can be used in combination of two or more.
• the above-mentioned reactive derivative is, for example, a structure derived from 2,6-dihalobenzonitrile, a compound capable of reacting with an aromatic dihydroxy compound represented by the following general formula. It means a compound derived by reacting two 2,6-dihalobenzonitriles or a 2,6-dihalobenzonitrile and an aromatic dihydroxy compound. (In the formula, R is the same as defined in general formula (1), and X is the same as defined in general formula (2).)
• the aromatic dihydroxy compound (I) is used in a molar ratio of 0.8 to 1.2 with respect to the dihalobenzonitrile compound (II). Among these, it is preferably used in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05, and more preferably in the range of 0.99 to 1.01. Especially preferred. In order to maximize the polymerization rate of the polycondensation reaction, it is preferred to use the aromatic dihydroxy compound (I) and the dihalobenzonitrile compound (II) at a molar ratio of substantially 1.00.
• each of the aromatic dihydroxy compound (I) and the dihalobenzonitrile compound (II) may be used in combination.
• the molar ratio of the total amount of each of the aromatic dihydroxy compound (I) and the dihalobenzonitrile compound (II) is used as described above.
• Base compound (III) any compound may be used regardless of whether it is an organic base or an inorganic base as long as it promotes the desalting polycondensation reaction and does not affect the quality, but an inorganic base is preferred. Among them, alkali metal compounds and alkaline earth metal compounds are preferred, and alkali metal compounds are particularly preferred.
• 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 (TBD) , 1,8-bis(dimethylaminonaphthalene) (DMAN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tert-butylimino-tri(pyrrolidino)phosphorane, tert-
• alkali metal compounds include alkali metals such as lithium, rubidium, cesium, potassium and sodium; hydrides such as lithium hydride, rubidium hydride, cesium hydride, potassium hydride and sodium hydride alkali metals; 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; Lithium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, potassium hydrogen carbonate and alkali metal hydrogen carbonate such as sodium hydrogen carbonate.
• the specific surface area of the alkali metal compound catalyst is preferably 0.8 m 2 /g or more, more preferably 1.2 m 2 /g or more.
• alkali metal carbonates such as lithium carbonate, rubidium carbonate, cesium carbonate, potassium carbonate and sodium carbonate are preferable, and lithium carbonate, potassium carbonate and carbonate Sodium is more preferable, and potassium carbonate and sodium carbonate having a specific surface area of 0.3 m 2 /g or more are particularly preferable from the viewpoint of availability.
• the amount of the basic compound (III) used is usually at least 2 mol times that of the dihydroxy compound (I) in terms of alkali metal ions contained. However, if it is used in large excess, side reactions such as cleavage of the generated ether bond may occur. It is more preferable to use , and it is particularly preferable to use within the range of 2 to 2.2 mol times.
• the polycondensation reaction method of the polyethernitrile in the present invention is not particularly limited, but for example, the aromatic dihydroxy compound (I) and the basic compound (III) are reacted in a solvent to obtain the aromatic dihydroxy compound (I) After obtaining a basic compound salt of, a method of subjecting the dihalobenzonitrile compound (II) to a desalting polycondensation reaction, an aromatic dihydroxy compound (I), a dihalobenzonitrile compound (II) and a basic compound A method of proceeding the desalting polycondensation reaction of the aromatic dihydroxy compound (I) and the dihalobenzonitrile compound (II) in the presence of (III).
• a compound represented by general formula (1) as aromatic dihydroxy compound (I) and a compound represented by general formula (2) as dihalobenzonitrile compound (II) in the presence of basic compound (III) is obtained.
• the reaction formula in this case is shown below. (Wherein, R is the same as defined in general formula (1), X and r are the same as defined in general formula (2), and Base means a basic compound (III).)
• the polycondensation reaction may be carried out using an alkali metal salt of the aromatic dihydroxy compound (I) and the dihalobenzonitrile compound (II) synthesized in advance.
• the polycondensation reaction may be divided into an oligomer formation step (A) and a polymerization step (B), and the reaction methods may be changed respectively, or the steps may not be divided.
• the oligomer-forming step (A) is a step of polycondensing the aromatic dihydroxy compound (I) and the dihalobenzonitrile compound (II) in the presence of the basic compound (III) to form an oligomer.
• oligomer There are no particular restrictions on the oligomer as used herein, but a polycondensation reaction product with a polymer reduced viscosity of less than 1 is referred to as an oligomer.
• the polymer-forming step (B) is a step of further subjecting the oligomer obtained in the step (A) to a polycondensation reaction to form a polymer.
• the polycondensation reaction product of step (A) can be used as it is, or an oligomer isolated by performing step (A) separately can be used.
• the polycondensation reaction includes an operation for removing water generated during the desalting reaction from outside the system. As an operation method thereof, for example, the reaction is carried out in the presence of a solvent that forms an azeotrope with water at a temperature at which the desalting reaction proceeds, and during this time water is distilled off from the reaction mixture with the solvent that forms an azeotrope with water.
• the temperature at which the desalting reaction starts is usually around 130° C., although it depends on the starting material.
• 4,4′-biphenol as the aromatic dihydroxy compound (I) and 2,6-dichlorobenzonitrile as the dihalobenzonitrile compound (II), potassium carbonate and sulfolane (boiling point 285) as the aprotic solvent. °C)
• the reaction temperature is preferably in the range of 130 to 170°C.
• the reaction system is substantially anhydrous, preferably less than 0.5% by weight.
• the polycondensation reaction is carried out under an inert atmosphere, such as a nitrogen atmosphere, under atmospheric pressure, but it may be carried out under pressure or under reduced pressure.
• a reaction solvent can be used in the polycondensation reaction, and an aprotic solvent is preferably used as the reaction solvent.
• aprotic solvents include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -butyrolactone, Sulfolane, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, diisopropylsulfone, diphenylsulfone, diphenyl ether, benzophenone, dialkoxybenzene (alkoxy group with 1 to 4 carbon atoms), trialkoxybenzene (alkoxy group with 1 to 4 carbon atoms) ) and the like.
• polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, sulfolane, diphenylsulfone and dimethylsulfoxide. These can be used singly or in combination of two or more. Additionally, nitrogen-containing solvents may be used, specifically dimethylacetamide, dimethylformamide, and N-alkylpyrrolidinones such as N-methylpyrrolidinone. Other solvents such as benzophenone and tetrasubstituted urea may also be used.
• the amount of the dipolar aprotic solvent to be used is not particularly limited as long as it dissolves the raw materials uniformly and the alkali metal salt is well dispersed by stirring.
• the amount should be selected so as to maximize the volumetric efficiency of the reactor for the raw material used and the target polymer. Usually, it is selected in the range of 0.5 to 20 times the total weight of the raw material and the alkali metal salt.
• Specific examples of solvents that form an azeotrope with water include aromatic hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole.
• a solvent that forms an azeotrope with water it is preferable to use a solvent that forms an azeotrope with water in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the aprotic solvent. From the viewpoint of volumetric efficiency and solvent recovery, the range of 1 to 10 parts by weight is more preferable, and the range of 2 to 5 parts by weight is even more preferable.
• the reaction temperature in the polycondensation reaction is in the range of 140°C to 300°C. Within this range, the reaction may be continued at a constant temperature, or the temperature may be raised as the polycondensation reaction proceeds.
• 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. More preferably, it is in the range of 155 to 165 ° C.
• the polymerization step (B) is preferably in the range of 200 to 300 ° C., preferably in the range of 210 to 270 ° C.
• aromatic dihydroxy compound (I) and 2,6-dichlorobenzonitrile as the dihalobenzonitrile compound (II)
• potassium carbonate and sulfolane as the aprotic solvent. ° C.
• toluene is used as a solvent that forms an azeotrope with water, a range of 190 to 280° C. is suitable.
• the reaction time of the polycondensation reaction depends on the reaction conditions and raw materials used, but it is usually 3 to 20 hours.
• the reaction time of the step (A) is preferably continued until the generation of carbon dioxide and water is almost completely eliminated. , is not particularly limited. It is usually 1 to 6 hours, preferably about 2 to 4 hours.
• Step (B) is 1 to 8 hours, preferably 1 to 7 hours, and more preferably 1 to 6 hours, although it cannot be generalized depending on the reaction conditions and raw materials used.
• the desired polyethernitrile molecular weight can also be controlled using monofunctional phenolic chain terminators such as p-phenylphenol, phenol, t-butylphenol, and the like to control the progress of the reaction.
• monofunctional phenolic chain terminators such as p-phenylphenol, phenol, t-butylphenol, and the like to control the progress of the reaction.
• the polymer is treated with an activated aromatic halide such as methyl halide, benzyl halide, or an aliphatic halide to form hydroxy-terminated polyethernitrile. Conversion of the groups to ether groups, which stabilize the polymer, is preferred as it can result in polymers with good melt and oxidation stability.
• Step 2 The step (step 2) of taking out the polymer obtained by the polycondensation reaction from the polycondensation reactor in the present invention will be described below.
• the polymer may be taken out by taking out the polycondensation reaction product as it is from the reaction apparatus after the completion of the polycondensation reaction. After that, after cooling and solidification, it may be pulverized and subjected to the next steps of washing, drying, and manufacturing of molding materials (pellets, chips), or it may be directly put into a washing tank for the washing step to be described later.
• the polymer may be taken out in a slurry state or a wax state by injecting a solvent used in the washing step described later into the reactor after the polycondensation reaction is completed. The polymer taken out in this way may be subjected to a washing process, a drying process, and a manufacturing process of a molding material (pellets, chips), which will be described later.
• Step 3 The step (step 3) in the present invention of removing the polymer remaining in the polycondensation reactor and supplying a new reaction solvent and reaction raw materials to the polycondensation reactor to perform a new polycondensation reaction will be described.
• the method for removing the polymer remaining in the polycondensation reactor includes, for example, the following method.
• the remaining polymer is removed by washing the inside of the system with a) a good solvent for the polymer (sulfolane, NMP, etc.) as used in the polycondensation reaction, b) washing (rinsing) with a solvent (acetone, methanol, etc.) which is a poor solvent for the polymer described later and is compatible with the polymerization solvent; It can be washed with distilled water or deionized water. If the water in c) is compatible with the washing solvent used in a), the step b) may be omitted. It is easy to choose what can be separated.
• the amount of solvent used and the number of times of washing are arbitrary as long as the amount of residual polymer is less than the desired amount.
• the amount of polymer remaining in the reactor can be calculated and confirmed from the amount of washing liquid used and the amount of polymer recovered in the washing liquid.
• the residual amount of the polymer after removing the polymer remaining in the reactor is the upper limit of the theoretical yield of the polymer obtained from the reaction raw materials supplied to the reactor when performing a new polycondensation reaction. is preferably 5000 ppm or less, more preferably 4000 ppm or less, and since the MFR reduction rate for a polymer without residue contamination is less than 10%, it is further preferably 3000 ppm or less, 1000 ppm The following are particularly preferred.
• the lower limit thereof is preferably as close to 0 as possible, but from the viewpoint of production efficiency, it is preferably 0.1 ppm or more, more preferably 1 ppm or more.
• the residual amount of the polymer described above is not particularly limited, but can be analyzed, for example, by the following method.
• Each of the washing solutions discharged after washing as described above is subjected to the following treatment, and the total amount of washed and discharged polymer is measured. It can be obtained by calculation.
• a) the discharged washing liquid extracted after washing with a good solvent for the polymer (a partial sample may be used if it is in a homogeneous state) is heated and evaporated to dryness to remove the solvent, washed with water and filtered to remove salts.
• the residue collected by the above is dried to remove moisture, and the amount of polymer is weighed.
• a new polycondensation reaction is performed by supplying a new reaction solvent and reaction raw materials to the polycondensation reactor, which means that the polymerization performed in step 1 is performed in the reactor after the residual polymer is removed. It means performing a new condensation reaction.
• the polycondensation reaction product obtained by the new polycondensation reaction can be similarly taken out from the reaction apparatus as in step 2 and subjected to the washing step and drying step described later.
• polycondensation reaction of polyethernitrile is performed in the reactor by the above method.
• Step 1 the polymer obtained by the polycondensation reaction is removed from the reactor by the above method (Step 2), and the polycondensation reaction product remaining in the reactor after removing the polymer is removed by the above method. It can be carried out by removing it and then conducting a new polycondensation reaction (step 3).
• step 3 the new polycondensation reaction can be carried out in the same manner as in step 1.
• step 1 when a continuous reactor is used as the polycondensation reactor and polyethernitrile is produced by continuous operation, polycondensation of polyethernitrile is performed in the reactor by the above method.
• the reaction is carried out (step 1), the polymer obtained by the polycondensation reaction is taken out from the reaction apparatus by the above method (step 2), while a new polycondensation reaction liquid flows into the reaction apparatus. This can be done by carrying out a new polymerization (step 3) while the residual polymer is removed.
• the production method of the present invention by going through steps 1, 2 and 3, polyethernitrile can be repeatedly produced in the same reactor, so this may be referred to as continuous production. That is, the production method of the present invention may be called a continuous production method.
• the polymer obtained by the polycondensation reaction can be washed to remove salts, reaction solvents and the like contained therein.
• This washing step (step 4) is performed by extracting and washing the reaction solvent in the polymer using a solvent such as alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, water, etc. in a known manner, and then preferably is preferably washed with water to remove the salt produced by the desalting reaction in the polymer.
• a solvent such as alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, water, etc.
• the polycondensation reaction product in a pulverized, slurry or wax state is transferred to a container equipped with a stirrer, and stirred and washed with a washing solvent until the content of the reaction solvent and salt is less than the target content. , repeat the filtration operation.
• a multifunctional filtration apparatus or the like capable of washing, filtering and drying with one apparatus may be used.
• alcohols other than water as extraction and washing solvents for the reaction solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, and n-amyl alcohol. , isoamyl alcohol, t-amyl alcohol, n-hexyl alcohol, cyclohexanol, n-octyl alcohol, capryl alcohol and the like.
• 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 and the like.
• aliphatic hydrocarbons examples include n-hexane, 2-methylheptane, 3-methylheptane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3 -saturation of methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, cyclohexane, etc.
• Examples include aliphatic hydrocarbons, unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene and cyclohexene.
• aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, t-butylbenzene, styrene, and allylbenzene. mentioned.
• methanol, ethanol, acetone, methyl ethyl ketone, xylene, toluene, and the like are preferable, and acetone and methanol are particularly preferable in terms of operability and ease of distillation recovery of the reaction solvent after washing.
• Water is preferable for washing the alkali metal salt such as potassium chloride produced in the desalting polycondensation reaction, and acidic water containing a low concentration of oxalic acid or acetic acid may be used.
• the amount of washing solvent used, the number of times of washing, and the washing temperature may be appropriately selected according to the amount of residual reaction solvent and residual alkali metal salt to be removed.
• the polymer can be dried.
• the water-containing polymer is dried by a known method.
• a known device such as an evaporator, a tray oven, or a tumbler can be used.
• the target moisture content is typically 0.5 wt% or less, preferably 0.4 wt% or less, more preferably 0.3 wt% or less.
• the conditions for this drying step may be any conditions as long as the temperature is below the melting point of the polymer and the water can be removed. It is preferable to carry out the reaction in an atmosphere of an inert gas (nitrogen, argon, etc.), under an inert gas stream, or under reduced pressure so as not to come into contact with air as much as possible.
• an inert gas nitrogen, argon, etc.
• the polyethernitrile obtained by the production method of the present invention has a melt flow rate (MFR) in the range of 2 to 50 g/10 minutes measured under a load of 5000 g at 390 ° C. in accordance with ISO 1133, and has a high flow rate when heated and melted. Since the heat-molded product exhibits excellent properties such as high heat resistance, surface smoothness, and dimensional stability, it is possible to obtain a stable thermoformed product with improved application quality.
• the melt flow rate (MFR) of the polyethernitrile obtained by the production method of the present invention is preferably in the range of 3 to 50 g/10 minutes, more preferably in the range of 4 to 50 g/10 minutes, and 5 to 50 g/10 minutes. Ranges are more preferred.
• the production method of the present invention even if the production of polyethernitrile is repeated in the same polycondensation reaction apparatus, the polyethernitrile obtained in the first polycondensation reaction and the polyether obtained in the second and subsequent polycondensation reactions It is possible to produce a polyethernitrile with a stable melt fluidity without a large difference in melt flow rate from that of nitrile.
• the molecular weight (number average molecular weight (Mn), weight average molecular weight (Mw)) of the polyethernitrile produced by the production method of the present invention is not particularly limited depending on the application. 000, preferably 50,000 to 500,000, more preferably 60,000 to 300,000. If the molecular weight of the obtained polymer is less than 40,000, the mechanical strength may be poor, and if it is 1,000,000 or more, moldability may become difficult.
• the reduced viscosity ⁇ red of the polyethernitrile produced by the production method of the present invention is in the range of 1 to 5, preferably in the range of 1.2 to 4.5, and 1.5 to 4.0. It is more preferably within the following range, and particularly preferably from 1.5 to 3.5.
• the reduced viscosity ⁇ red in the present invention is a value measured by the method described in the measurement method of Examples described later.
• this powder can be used to produce molding materials (pellets, chips) for producing moldings.
• the method for producing a molding material by heating and melting this polyethernitrile powder is not particularly limited, but it is preferable to carry out under oxygen shielding or in an inert atmosphere such as nitrogen.
• melt-kneading equipment such as single-screw, twin-screw or multi-screw extruders, Banbury mixers, kneaders, and rollers are used as molding equipment for producing molding materials such as pellets and chips.
• a sheet produced using a machine may be cut to produce molding materials such as pellets and chips.
• An industrially preferred process for producing molding materials is as follows.
• the polyethernitrile powder that has been subjected to polycondensation, pulverization, washing and vacuum drying is directly transferred and stored in a silo or the like sealed with nitrogen gas or the like without being exposed to the outside air.
• it is molded into pellets or chips, it is transferred to an extruder together with nitrogen gas through a pipe. Then, without contact with oxygen (air), melt-kneading is performed, and the molten polymer from the die is cut underwater or the strand is water-cooled and cut for pelletizing.
• the melt processing conditions are a temperature sufficient to melt the polymer, and the above operation is performed.
• the upper limit of the temperature during melt processing is 500° C. or less.
• the polyethernitrile powder using biphenol used in the examples had a melting point of 364°C, it is preferable to process at a temperature higher than 380°C. C. or less, more preferably 450.degree. C. or less, even more preferably 430.degree. C. or less, and particularly preferably 400.degree.
• a polyethernitrile powder or a molding material obtained by the production method of the present invention is mixed with at least one selected from the group consisting of a thermoplastic resin material (A), an additive (B), and a filler (C). may be used as a polyethernitrile resin composition.
• polyethernitrile resin composition In the case of producing a polyethernitrile resin composition, it can be carried out in the same manner as in the process for producing the molding material described above, and the mixing of each component is performed by: 1) polyethernitrile powder or preformed A method of premixing a polyethernitrile molding material and other components (above-mentioned (A) to (C)) and then transferring it to an extruder, 2) polyethernitrile powder or preformed polyethernitrile molding Materials and other components (above (A) to (C)) are used to prepare molding materials of a plurality of polyethernitrile resin compositions having different compositions in advance, and the molding materials are mixed with a desired content ratio.
• thermoplastic resin material (A) contained in the polyethernitrile resin composition include, for example, high-density polyethylene, medium-density polyethylene, isotactic polypropylene, acrylonitrile-butadiene-styrene (ABS) resin, Acrylonitrile/styrene (AS) resin, acrylic resin, fluorine resin (polytetrafluoroethylene, etc.), polyester, polycarbonate, polyarylate, aliphatic polyamide, aromatic polyamide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone , polyphenylene sulfide, polyetherimide, polyamideimide, polyesterimide, and modified polyphenylene oxide.
• ABS acrylonitrile-butadiene-styrene
• AS Acrylonitrile/styrene
• acrylic resin polytetrafluoroethylene, etc.
• polyester polycarbonate, polyarylate, aliphatic polyamide, aromatic polyamide
• additive (B) contained in the polyethernitrile resin composition include, for example, a hydrophilic agent, an antioxidant, a secondary antioxidant, a flame retardant, a flame retardant aid, a plasticizer, and a lubricant.
• release agent anti-fogging agent, weather stabilizer, light stabilizer, hydrolysis resistance improver, fluidity improver, ultraviolet absorber, antistatic agent, metal deactivator, near-infrared absorber, coloring agents (dyes, pigments).
• the filler (C) contained in the polyethernitrile resin composition include various metal powders, inorganic acid metal salts (calcium carbonate, zinc borate, calcium borate, zinc stannate, sulfuric acid, calcium, barium sulfate, etc.) powder, metal oxide (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.) powder, metal hydroxide (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina water Boehmite, etc.) powder, metal sulfide (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.) powder, silver nanowire, carbon fiber, glass fiber, carbon nanotube, graphene, ceramic materials such as silica. These (A) to (C) can be blended in appropriate amounts depending on the purpose of use. These (A ) to (C) is preferably 90% by weight or less of the total weight of the polyethernitrile resin composition
• the polyethernitrile obtained by the method of the present invention can be used as a molding material by the above-described method, can be used for manufacturing molded articles and parts using it, and has heat resistance, chemical resistance, and flame retardancy. and high mechanical properties.
• it can be used for electric and electronic applications such as personal computers and semiconductor parts, for automotive applications such as gears, bearings, and housings around engines, for medical equipment, and for applications in the aerospace field. can be manufactured to
• the analysis method in the present invention is as follows.
• ⁇ Analysis method> (1) Method for measuring reduced viscosity ⁇ red (dL/g) 0.1 g of a sample was dissolved in about 5 g of parachlorophenol at 180°C, transferred to a 10 mL volumetric flask, and diluted to volume at 40°C. A 5 mL whole pipette was used to make a constant volume of this, and it was placed in an Ostwald tube (capillary tube 0.75 mm). The Ostwald tube was allowed to stand in a constant temperature bath at 40.0° C.
• ⁇ Reference example 1> A four-necked 3 L reactor (material SUS316L) was equipped with a mechanical stirrer, thermometer, dry nitrogen inlet, reflux and bottom valve. The reactor, stirrer, and reflux vessel were unused, and were installed after being manually washed with water, degreased with acetone, and dried. 298.45 g (1.735 mol) of 2,6-dichlorobenzonitrile (hereinafter abbreviated as DCBN) and 323.08 g (1.735 mol) of 4,4′-biphenol (hereinafter abbreviated as BP) were added to this reactor.
• DCBN 2,6-dichlorobenzonitrile
• BP 4,4′-biphenol
• the polymerization reactant was allowed to stand at 220° C. by opening the valve at the bottom of the reactor, withdrawing the polymerization reactant, and allowing it to cool and solidify.
• the amount of the polymerized reaction product discharged was 98% by weight with respect to the theoretical yield of the polymer obtained from the raw materials used, and the polymer remained in the reactor.
• the extracted solid product was pulverized with a Waring blender, washed several times with acetone and distilled water, and dried in a vacuum oven at 120° C. for 16 hours to obtain 470 g of polyethernitrile powder. (97% yield based on the polymerization reactant withdrawn).
• the reduced viscosity ⁇ red of this polymer powder was 2.19.
• the weight average molecular weight (Mw) measured by GPC was 77,300, and the number average molecular weight (Mn) was 30,100.
• the MFR of this polyether powder was 11.5 (g/10min).
• Example 1 After withdrawing the polymerization reaction product of Comparative Example 1, 500 g of N-methyl-2-pyrrolidone (NMP) was added to the reactor in which 2 wt% of the polymerization reaction product remained with respect to the charged amount, and the mixture was heated at 200°C for 30 minutes. While stirring, NMP was refluxed in the reactor for 1 minute to wash the entire inner surface of the reactor. After the washing liquid was discharged from the bottom valve, the same operation was repeated once more. Next, 2 L of acetone was added, and the acetone was refluxed in the reactor while heating and stirring to wash the entire inner surface of the reactor, and the reactor was discharged from the bottom valve.
• NMP N-methyl-2-pyrrolidone
• a polyethernitrile was obtained in the same manner as in Reference Example 1 using this cleaned reactor.
• the reduced viscosity ⁇ red of this polymer powder was 2.17.
• the weight average molecular weight (Mw) measured by GPC was 76,700, and the number average molecular weight (Mn) was 32,800.
• the MFR of this polyether powder was 11.5 (g/10 min), and compared with Reference Example 1, no decrease in MFR was observed.
• Example 2 In Example 1, the remaining polymerization reaction product after extraction was collected, and after washing the reactor in the same manner as in Example 1, the raw materials and solvent were charged in the same manner as in Reference Example 1, and the collected polymerization reaction. 0.3 wt % (3000 ppm) of the theoretical yield was added, polymerized, extracted and washed in the same manner as in Reference Example 1 to obtain polyethernitrile and measure the MFR. The MFR was 10.6 (g/10 min), and compared with Reference Example 1, the reduction rate of MFR was 8% within 10%.

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