The present invention relates to a method for continuously producing aromatic polyether.
Background technology
[0002]
　Aromatic polymers such as polyphenylsulfone (PPSU), polysulfone (PSU), polyethersulfone (PES), polyetheretherketone (PEEK), polyethernitrile (PEN) and polyetherimide (PEI) are heat resistant. Excellent in chemical resistance, flame retardancy, mechanical strength, electrical characteristics and dimensional stability. Since these aromatic polymers can be molded into various molded products, films, sheets, fibers, etc. by general melt processing methods such as extrusion molding, injection molding, and compression molding, electrical equipment, electronic equipment, and automobile equipment. And is widely used in a wide range of technical fields such as packaging materials.
[0003]
　As a polymerization method of aromatic polyetherketone (PAEK) such as PEEK, for example, the polymerization method described in Patent Document 1 is known as a prior art. Patent Document 1 describes a method for producing PAEK by a nucleophilic substitution reaction using an aromatic dihalide component, an aromatic dihydroxy component, an alkali metal carbonate or a bicarbonate, and a solvent.
Prior art literature
Patent documents
[0004]
Patent Document 1: Japanese Patent Publication No. 61-10486
Outline of the invention
Problems to be solved by the invention
[0005]
　The production of the polymer generally includes a production using a batch method and a production using a continuous method. For example, in the case of manufacturing using a continuous method, raw materials and the like are supplied into the continuous manufacturing apparatus in a liquid form from the viewpoint of quantitativeness and liquid feeding property.
[0006]
　However, in the polymerization of aromatic polyethers such as PAEK, production using a batch method has been conventionally performed. Further, in the polymerization of aromatic polyether, if water is contained in the raw material, the polymerization reaction due to the nucleophilic substitution reaction is inhibited, so it is desirable not to use water in the supply of the raw material. Alternatively, it is desired to dehydrate the raw material as necessary or remove the water generated during the reaction.
[0007]
　Therefore, in order to produce PAEK by a nucleophilic substitution reaction in a continuous manner, it can be said that it is necessary to supply the raw material without using water. However, if water is not used and the supply is attempted, the piping is likely to be clogged due to the influence of the alkali metal compound that is insoluble in the organic solvent. As a result, handling such as transportability becomes complicated, and high-concentration raw materials cannot be supplied, so that there is a concern that the production efficiency of the polymer may decrease.
[0008]
　An object of the present invention is to realize a manufacturing method capable of stably obtaining aromatic polyether by suppressing blockage of piping of a continuous manufacturing apparatus.
Means to solve problems
[0009]
　In order to solve the above problems, the method for continuously producing an aromatic polyether according to the present invention
　supplies a polymerization solvent, an alkali metal compound and a raw material into a continuous production apparatus in which a plurality of reaction tanks are sequentially connected. A step,
　a polymerization step of forming a reaction mixture by carrying out a polymerization reaction in the polymerization solvent in at least one of the reaction tanks, and
　a moving step of sequentially moving the reaction mixture to each reaction tank.
　It is a method for continuously producing an aromatic polyether, which is carried out in parallel and supplies the alkali metal compound as an aqueous mixture.
The invention's effect
[0010]
　According to one aspect of the present invention, blockage of the piping of the continuous manufacturing apparatus is suppressed, and aromatic polyether can be stably obtained.
Embodiment for carrying out the invention
[0011]
　[Aromatic polyether]
　The aromatic polyether obtained by the continuous production method of the aromatic polyether according to the present embodiment (hereinafter, may be simply abbreviated as "the continuous production method of the present embodiment") is at least aromatic. It is an aromatic polymer in which a group ring and an ether group are linked, and also includes the aromatic polymer containing a sulfone group and / or a ketone group, a nitrile group, and the like. Among the aromatic polyethers, the continuous production method of the present embodiment is suitable for producing polyaryletherketone (aromatic polyetherketone, PAEK), aromatic polysulfone (PASF) and aromatic polyethernitrile (PAEN). In the present specification, when it has a plurality of groups selected from a sulfone group, a ketone group and a nitrile group, it is classified as an aromatic polymer having a large number of moles. Specifically, when the aromatic polyether has both a sulfone group and a ketone group, when the number of moles of the ketone group is larger than the number of moles of the sulfone group, the aromatic polyether is PAEK and less than the number of moles of the sulfone group. When it is classified as PASF.
[0012]
　The PAEK obtained by the continuous production method of the present embodiment is not particularly limited, and has a divalent aromatic group (residue obtained by removing two hydrogen atoms bonded to the aromatic ring from the aromatic compound), a carbonyl group and a carbonyl group. It has a structure consisting of repeating units containing an ether group. Examples of PAEK include polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK), and the like. Be done.
[0013]
　The PASF obtained by the continuous production method of the present embodiment typically contains a divalent aromatic group (a residue obtained by removing two hydrogen atoms bonded to the aromatic ring from the aromatic compound) and a sulfonyl compound. A resin having a repeating unit containing a group (-SO 2- ). Examples of PASF include polysulfone (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES) and the like.
[0014]
　The PAEN obtained by the continuous production method of the present embodiment typically contains a divalent aromatic group to which a cyano group is bonded (from an aromatic compound to which a cyano group is bonded to two hydrogen atoms bonded to the aromatic ring). It is a resin having a repeating unit containing an ether group (—O—) and a residue (excluding the residue). Examples of PAEN include polyether nitrile (PEN) and the like.
[0015]
　The continuous production method of the present embodiment is a PAEK, which can be obtained by a polycondensation reaction accompanied by the formation of a by-product salt, that is, a desalting polycondensation reaction, because the effect of the present application can be easily obtained and the production is easy. Suitable for the production of PSU, PPSU, PES or PAEN.
[0016]
　The weight average molecular weight (Mw) of the aromatic polyether obtained by the continuous production method of the present embodiment is wide. Usually, the lower limit of the weight average molecular weight of the aromatic polymer obtained by the present embodiment by gel permeation chromatography (GPC) is 3,000 or more, preferably 5,000 or more, more preferably 10,000 or more. be. The upper limit of the weight average molecular weight is 300,000 or less, preferably 200,000 or less.
[0017]
　Here, Mw is a polystyrene-equivalent value, and the solvent, column, measurement temperature, and the like can be appropriately selected depending on the type of the target aromatic polyether.
[0018]
　(Measuring method
　of weight average molecular weight ) 1) Weight average molecular weight (Mw) of PAEK polymer
　Measure under the following conditions using GPC.
Solvent: 4-chlorophenol / 1,2-dichlorobenzene = 30/70 (wt%),
temperature: 40 ° C.,
detector: RI detector
sample injection volume: 200 μL (concentration: 30 mg / 10 mL),
flow velocity: 0. 5 mL / min,
standard polystyrene: 1,090,000,000, 427,000, 96,400, 37,900, 17,400, and 5,560 standard polystyrenes.
[0019]
　2) Weight average molecular weight (Mw) of PASF and PAEN Measured
　under the following conditions using GPC.
Solvent: LiBr 0.01M / L NMP solution,
temperature: 40 ° C,
detector: RI detector,
sample injection volume: 100 μL (concentration: 1 mg / 1 mL),
flow velocity: 1.0 mL / min,
standard polystyrene: 427,000. , 96,400, 37,900, 17,400, and 5,560 standard polystyrenes.
[0020]
　[Continuous Manufacturing Method] In the continuous manufacturing method of the
　present embodiment, the following supply step, polymerization step, and moving step are simultaneously performed in parallel in a continuous manufacturing apparatus in which a plurality of reaction tanks are sequentially connected. Hereinafter, the continuous manufacturing apparatus and each process will be described.
[0021]
　Before explaining each process, the continuous manufacturing apparatus will be described first. In the continuous manufacturing apparatus used in the continuous manufacturing method of the present embodiment, a plurality of reaction tanks are sequentially connected. In terms of resource saving, energy saving, equipment cost reduction, etc., the continuous manufacturing equipment is provided with a storage chamber for accommodating a plurality of reaction tanks, the reaction tanks are sequentially connected, and the reaction tanks are connected via a gas phase in the storage chamber. Therefore, it is preferable that the equipment is a continuous manufacturing apparatus that communicates with each other. Alternatively, as a modification of the continuous manufacturing apparatus, a plurality of independent reaction tanks are sequentially connected downward in the vertical direction, and the gas phase portion of each reaction tank may be a continuous manufacturing apparatus that communicates with each other via a ventilation portion. preferable. The number of reaction tanks is preferably 3 or more because a polymer having a high degree of polymerization can be easily obtained. Further, from the viewpoint of compactness and economy of the continuous manufacturing apparatus, the number of reaction tanks is preferably 30 or less, and preferably 20 or less.
[0022]
　The preferred continuous manufacturing apparatus is, for example, a continuous manufacturing apparatus having the same apparatus configuration as the continuous manufacturing apparatus for polyarylene sulfide disclosed in International Publication No. 2017/179327 and International Publication No. 2018/159220. obtain. In the preferred continuous manufacturing apparatus, since the gas phase portions of the plurality of reaction tanks communicate with each other, the pressure of each gas phase portion becomes uniform. Therefore, since water can be removed from any of the plurality of reaction tanks by the dehydration section connected to the continuous production apparatus, the water in the reaction mixture increases from the upstream side to the downstream side in the moving direction of the reaction mixture. The amount will be small. As a result, the reaction inhibition by water is suppressed and the polymerization reaction is promoted. Further, since the boiling point of the reaction mixture rises, polymerization at a high temperature becomes possible, and the polymerization reaction can be further promoted. Then, by promoting the above-mentioned polymerization reaction, the temperature of the reaction mixture is likely to rise, and the polymerization reaction is more likely to be promoted.
[0023]
　[Supply step] In the
　supply step, the polymerization solvent, the alkali metal compound and the raw material are supplied into the above-mentioned continuous manufacturing apparatus.
[0024]
　(Polymerization solvent)
　Examples of the polymerization solvent include N, N-dialkylformamides such as N, N-dimethylformamide (DMF), N, N-diethylformamide and N, N-dipropylformamide; N, N-dimethylacetamide. , N, N-dialkylacetamides such as N, N-diethylacetamide and N, N-dipropylacetamide; N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone. And N-alkyl-2-pyrrolidone such as N-cyclohexyl-2-pyrrolidone; such as N, N'-dimethylimidazolidinone, N, N'-diethylimidazolidinone and N, N'-dipropylimidazolidinone. N, N'-dialkylimidazolidinone; N-alkylcaprolactams such as N-methylcaprolactam, N-ethylcaprolactam and N-propylcaprolactam; Sulfones such as sulfones; sulfones such as dimethylformamide and diethylsulfoxide; and mixed solvents selected from the group consisting of mixtures thereof can be mentioned. As the polymerization solvent, a solvent in which each or a mixture is liquid at room temperature is preferable.
[0025]
　Furthermore, it is preferable to use a polymerization solvent selected from the group consisting of N-alkyl-2-pyrrolidone, N-alkylcaprolidone, N, N'-dialkylimidazolidinone, N-alkylcaprolidone and sulfone and mixtures thereof. , N-alkyl-2-pyrrolidone, sulfone and polymerization solvents selected from the group consisting of mixtures thereof are more preferred, with sulfolanes, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and their mixtures. It is more preferred to use a polymerization solvent selected from the group consisting of mixtures.
[0026]
　(Alkali metal compound) The
　alkali metal compound may be any compound as long as it can convert the aromatic dihydroxy compound described later into an alkali metal salt. Here, examples of the alkali metal compound include carbonates of lithium, sodium, potassium, rubidium or cesium, or hydrogen carbonates or hydroxides. As the alkali metal compound, a sodium or potassium compound is preferable, and an alkali metal carbonate is preferable. As the alkali metal compound, sodium carbonate and potassium carbonate are more preferable. Only one kind of these alkali metal compounds may be used, or two or more kinds may be used in combination depending on the case. It is appropriate to select the amount of the alkali metal compound to be used in the range of 1.01 to 2.5 equivalents with respect to 1 equivalent of the aromatic dihydroxy compound to be used. In addition, 1 mol corresponds to 2 equivalents of each of the aromatic dihydroxy compound and the alkali metal carbonate, and 1 mol corresponds to 1 equivalent of each of the alkali metal hydrogen carbonate and the hydroxide.
[0027]
　In the continuous production method of the present embodiment, the alkali metal compound is supplied into the continuous production apparatus as an aqueous mixture, that is, a mixture with fluid water. The water-insoluble raw material may be supplied as a mixture with the polymerization solvent into the continuous production apparatus separately from the aqueous mixture. The aqueous mixture may contain a raw material such as a monomer described later. Based on the conventional method, it was considered that when the alkali metal compound was supplied as an aqueous mixture, the reaction was inhibited because water was contained in the polymerization system. However, the present inventors have found that in the continuous production method using the above-mentioned continuous production apparatus, the polymerization proceeds without inhibiting the reaction even if it contains water. Then, by supplying the alkali metal compound as an aqueous mixture, it is possible to suppress the blockage of the piping of the continuous manufacturing apparatus and the solidification of the raw materials and the like in the continuous manufacturing apparatus. Further, by supplying the aqueous mixture separately from the mixture of a part of the water-insoluble raw material and the polymerization solvent into the continuous production apparatus, it is possible to further suppress the blockage of the pipe. Examples of the aqueous mixture include an aqueous slurry and an aqueous solution, and an aqueous solution is preferable.
[0028]
　(Raw Material)
　Examples of the raw material include aromatic dihalogen compounds and aromatic dihydroxy compounds which are monomers of aromatic polyether.
[0029]
　In the continuous production method, the raw material is supplied in a liquid state, but it is preferable to supply the raw material into the continuous production apparatus in the form of a solution that dissolves in the polymerization solvent in terms of quantification and liquid feeding property. In the present specification, the liquid means a solution, a dispersion or a slurry. Further, the solution means a state in which a solid is uniformly dissolved in a solvent. The solvent may be an aqueous solvent such as water, an organic solvent, or a mixture thereof.
[0030]
　When the raw material is supplied in the form of a solution, if water is contained in the solution of the polymerization solvent and the raw material, at least a part thereof may be dehydrated before being supplied into the continuous production apparatus.
[0031]
　<< Raw Material
　of PAEK >> When the aromatic polyether produced is PAEK, for example, JP-A-61-10486, JP-A-7-138360, International Publication No. 2003/050163, JP-A-2010-70657, for example. And it can be produced by using the raw materials described in Japanese Patent Publication No. 2014-532109 and the like.
[0032]
　Examples of the aromatic dihalogen compound include an aromatic ring, a ketone group (-CO-), and two halogens in one aromatic molecule such as 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone. Aromatic dihalide compounds having a group (eg, dihalogenated benzophenone) can be exemplified, but are not limited thereto.
[0033]
　Examples of the aromatic dihydroxy compound include 1,3-dihydroxybenzene (resorcin), 1,4-dihydroxybenzene (hydroquinone), 4,4'-dihydroxybiphenyl (4,4'-biphenol), and 4,4'-. Dihydroxyterphenyl, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone and 4,4'-tetraphenyl Examples of bisphenol and the like can be exemplified, but the present invention is not limited to these, and various diphenols such as bisphenol A and the like can be used in addition to these.
[0034]
　Further, the same polycondensation reaction can be carried out on a compound having an aromatic ring, a ketone group (-CO-), a halogen group and a hydroxyl group in one molecule. Examples of the compound that can be used in this reaction include compounds such as 4-hydroxy-4'-fluorobenzophenone and 4-hydroxy-4'-chlorobenzophenone.
[0035]
　When the aromatic polyether to be produced is PAEK, it is preferable that the aromatic dihalogen compound is mixed with the polymerization solvent and supplied into the continuous production apparatus. Further, it is preferable to mix the alkali metal compound and the aromatic dihydroxy compound with water and supply the mixture as an aqueous mixture such as an aqueous solution. This is because the polymerization reaction activity of the aromatic dihydroxy compound is increased by the neutralization reaction between the alkali metal compound and the aromatic dihydroxy compound. As a result, the reaction with the aromatic dihalogen compound is started immediately after being put into the continuous production apparatus, and a high molecular weight PAEK can be obtained. Further, by mixing the alkali metal compound and the aromatic dihydroxy compound with water and supplying the mixture as an aqueous mixture such as an aqueous solution, the alkali metal compound does not precipitate in a lump in the continuous production apparatus, and the load on the continuous production apparatus is increased. It can be suppressed.
[0036]
　<< Raw Material of PASF >> When the
　aromatic polyether to be produced is PASF, it can be produced using, for example, the raw material described in JP2013-159641.
[0037]
　Examples of the aromatic dihalogen compound include aromatic dihalogenosulfone compounds such as bis (4-chlorophenyl) sulfone (also referred to as dichlorodiphenyl sulfone) and 4,4'-bis (4-chlorophenylsulfonyl) biphenyl. The aromatic dihalogenosulfone compound may be any compound having an aromatic ring, a sulfonyl group (-SO 2- ), and two halogen groups in one molecule .
[0038]
　Examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone and bis (4-hydroxy-3-phenylphenyl) sulfone, 2,2-. Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide and bis (4-) Hydroxyphenyl) ether, hydroquinone, resorcin, catechol, phenylhydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,5,3', 5'-tetramethyl-4,4'-dihydroxybiphenyl , 2,2'-Diphenyl-4,4'-dihydroxybiphenyl and 4,4'-dihydroxy-p-quarterphenyl. The aromatic dihydroxy compound may be any compound having an aromatic ring and two hydroxyl groups in one molecule. In this embodiment, instead of all or part of the aromatic dihalogenosulfone compound and the aromatic dihydroxy compound, a halogeno group and a hydroxyl group in the molecule such as 4-hydroxy-4'-(4-chlorophenylsulfonyl) biphenyl are used. Compounds having a group can also be used.
[0039]
　Further, the same polycondensation reaction can be carried out with respect to a compound having an aromatic ring, a sulfonyl group (-SO 2- ), a halogen group and a hydroxyl group in one molecule . Examples of the compound that can be used in this reaction include compounds such as 4- (4-fluorobenzenesulfonyl) phenol and 4- (4-chlorobenzenesulfonyl) phenol.
[0040]
　<< Raw Material of PAEN >> When the
　aromatic polyether to be produced is PAEN, it can be produced using, for example, the raw material described in JP-A-7-138360.
[0041]
　That is, PAEN in the present invention uses an aromatic dihalide compound and an aromatic dihydroxy compound as conventionally known raw material monomers, and is a basic alkali capable of forming a phenolate type salt with the aromatic dihydroxy compound in a polymerization solvent. It is produced by desalting and polycondensing with an alkali metal carbonate, an alkali metal hydrogen carbonate or an alkali metal hydroxide which are metal compounds.
[0042]
　Examples of the aromatic dihalide compound include 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,4-difluorobenzonitrile, 2,4-dichlorobenzonitrile, and the like. Not limited to.
[0043]
　As the aromatic dihydroxy compound, those listed in the above-mentioned raw materials for PAEK can be used.
[0044]
　Further, the same polycondensation reaction can be carried out with respect to an aromatic ring having a nitrile group (-CN) in one molecule and a compound having a halogen group and a hydroxyl group. Examples of the compound that can be used in this reaction include 2-hydroxy-6-fluorobenzonitrile, 2-hydroxy-6-chlorobenzonitrile, 2-hydroxy-4-fluorobenzonitrile, and 2-hydroxy-4-chloro. Examples include compounds such as benzonitrile.
[0045]
　There are three raw material supply lines for continuous manufacturing equipment disclosed in WO 2017/179327 and WO 2018/159220. In the present embodiment, the aqueous solution of the alkali metal compound and the raw material are supplied from at least two supply lines including a line for supplying the aqueous solution of the alkali metal compound and another line for supplying the raw material. Is preferable.
[0046]
　In the present embodiment, the supply amount of the polymerization solvent, the alkali metal compound, and the raw material supplied in the continuous production apparatus can be appropriately changed depending on the volume of the continuous production apparatus, the intended production amount, and the like.
[0047]
　In the present embodiment, only one type of aromatic dihalogen compound, aromatic dihydroxy compound, and aromatic compound having a halogen group and a hydroxyl group is used depending on the type of the target aromatic polyether. Also, two or more kinds may be used in combination.
[0048]
　In the present embodiment, the molar ratio of the hydroxyl group to the halogen group is an important factor that determines the degree of polymerization. The molar ratio of the hydroxyl group to the halogen group is preferably in the range of hydroxyl group: halogen group = 0.8 to 1.2: 1.2 to 0.8, and hydroxyl group: halogen group = 0.9 to 1.1. More preferably, it is in the range of 1.1 to 0.9.
[0049]
　In the present embodiment, the number of moles of the aromatic dihydroxy compound with respect to 1 mol of the aromatic dihalogen compound supplied in the continuous production apparatus is preferably 0.90 to 1.10, more preferably 0.92 to 1.08. , 0.94 to 1.06 are more preferable.
[0050]
　In the present embodiment, when the polycondensation reaction is carried out, one or more bases having a valence of n (n is an integer of 1 or more) are blended, and the number of moles of the base with respect to 1 mol of the aromatic dihydroxy compound is set as a base. It is preferable to adjust so that the total value obtained by multiplying by n / 2 for each type is preferably 0.95 to 1.15, more preferably 1.00 to 1.10. n is, for example, 2 when the base is sodium carbonate and 1 when the base is sodium hydrogen carbonate or sodium hydroxide.
[0051]
　[Polymerization Step] In the
　polymerization step, a reaction mixture is formed by carrying out a polymerization reaction in at least one reaction tank in a polymerization solvent. The polymerization reaction carried out by the continuous production method of the present embodiment is typically a desalting polycondensation reaction by an aromatic nucleophilic substitution reaction.
[0052]
　When the aromatic polyether obtained by the continuous production method of the present embodiment is PAEK or PAEN, the polymerization temperature is preferably more than 100 ° C. and 320 ° C. or lower, and preferably 150 ° C. or higher and 300 ° C. or lower. More preferably, it is 170 ° C. or higher and 280 ° C. or lower. When the aromatic polyether obtained by the continuous production method of the present embodiment is PASF, the polymerization temperature is preferably more than 100 ° C. and 290 ° C. or lower, and more preferably 150 ° C. or higher and 270 ° C. or lower. , 170 ° C. or higher and 250 ° C. or lower are more preferable. The polymerization temperature is the temperature under pressurized conditions.
[0053]
　Further, the polymerization reaction is preferably carried out at a gauge pressure of more than 0 MPa, 1.0 MPa or less, preferably 0.7 MPa or less, and more preferably 0.5 MPa or less. It is preferable that the pressure in each reaction vessel of the continuous production apparatus is uniform in terms of accelerating the polymerization reaction and the like.
[0054]
　The pH of the reaction mixture in at least one reaction vessel is preferably 9 or more and 12.5 or less, preferably 9.5 or more and 12 or less, in terms of obtaining a high-molecular-weight aromatic polyether and suppressing precipitation of alkali metal compounds. Is more preferable, and 10 or more and 11.5 or less are further preferable. The pH can be adjusted, for example, by changing the amount of the alkali metal compound used, or by adding a strong base such as sodium hydroxide and potassium hydroxide to the aqueous solution of the alkali metal compound. be able to.
[0055]
　(Method for measuring pH)
　Water is added to 1 g of the reaction mixture to dilute it to 10 g, and then the pH is measured at 23 ° C. using a pH meter.
[0056]
　Further, in at least one reaction vessel, the reaction mixture contains the aromatic polyether having a weight average molecular weight of 2,000 or more and 50,000 or less, and the reaction mixture in at least one of the at least one reaction vessel. The pH of the above is preferably 9 or more and 12.5 or less, more preferably 9.5 or more and 12 or less, and further preferably 10 or more and 11.5 or less. That is, when the pH of the reaction mixture containing the aromatic polyether during the polymerization reaction is within the above range, a high molecular weight aromatic polyether can be obtained. In all reaction tanks, if the pH is lower than the above range, the polymerization reaction will not proceed, and if the pH is higher than the above range, an unfavorable side reaction will occur and a high molecular weight aromatic polyether cannot be obtained.
[0057]
　[Movement step] In the
　movement step, the reaction mixture is sequentially moved to each reaction tank. That is, the reaction mixture sequentially moves through a plurality of reaction tanks that are sequentially connected while advancing the polymerization reaction.
[0058]
　[Other Steps]
　The continuous production method of the present embodiment may include other steps in addition to the supply step, the polymerization step, and the transfer step. Examples of other steps include a recovery step of recovering the reaction mixture. It is preferable to perform the supply step, the polymerization step, the transfer step and the recovery step in parallel.
[0059]
　When recovering the reaction mixture, it is preferable to recover the reaction mixture in a slurry state by controlling the mass ratio of the monomer as a raw material to the polymerization solvent. The mass ratio of the monomer / polymerization solvent is usually 1 to 25 parts by mass, preferably 3 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the polymerization solvent. The polymerization solvent may be supplied from the middle of the polymerization reaction to the recovery, preferably from the end of the polymerization reaction to the recovery so that the mass ratio of the raw material monomer / the polymerization solvent is within the above range. By controlling the mass ratio of the monomer to the polymerization solvent in the above range, the problem of solidification of the reaction mixture at the time of recovery of the reaction mixture can be solved. In addition, the obtained aromatic polyether can be easily washed and the polymerization solvent and the like can be easily recovered or recycled.
[0060]
　[Summary]
　The method for continuously producing an aromatic polyether according to the present embodiment includes at least one of a supply step of supplying a polymerization solvent, an alkali metal compound and a raw material into a continuous production apparatus in which a plurality of reaction tanks are sequentially connected. In the above reaction tank, a polymerization step of forming a reaction mixture by carrying out a polymerization reaction in the polymerization solvent and a moving step of sequentially moving the reaction mixture to each reaction tank are carried out in parallel at the same time. The alkali metal compound is supplied as an aqueous mixture.
[0061]
　Further, in the method for continuously producing an aromatic polyether according to the present embodiment, the continuous production apparatus is different from a mixture in which the aqueous mixture containing at least the alkali metal compound is composed of at least a part of the raw material and the polymerization solvent. It is preferable that it is supplied inside.
[0062]
　Further, the method for continuously producing an aromatic polyether according to the present embodiment is preferably in the form of a solution in which the raw material is dissolved in the polymerization solvent.
[0063]
　Further, in the method for continuously producing aromatic polyether according to the present embodiment, it is preferable that the pH of the reaction mixture in at least one or more reaction tanks is 9 or more and 12.5 or less.
[0064]
　Further, the method for continuously producing an aromatic polyether according to the present embodiment contains the aromatic polyether having a weight average molecular weight of 2,000 or more and 50,000 or less in the reaction tank at least one of the reaction tanks. It is preferable that the pH of the reaction mixture in at least one of the at least one reaction tank is 9 or more and 12.5 or less.
[0065]
　Further, the method for continuously producing an aromatic polyether according to the present embodiment preferably contains an aromatic dihalogen compound and an aromatic dihydroxy compound as the raw materials.
[0066]
　Further, in the method for continuously producing an aromatic polyether according to the present embodiment, it is preferable that the alkali metal compound contains an alkali metal carbonate.
[0067]
　Further, in the method for continuously producing an aromatic polyether according to the present embodiment, it is preferable that the aromatic polyether is a polyaryletherketone.
[0068]
　Further, in the method for continuously producing aromatic polyether according to the present embodiment, it is preferable that the polyaryletherketone is a polyetheretherketone.
[0069]
　Further, in the method for continuously producing an aromatic polyether according to the present embodiment, it is preferable that the aromatic polyether is an aromatic polysulfone.
[0070]
　Further, in the method for continuously producing aromatic polyether according to the present embodiment, it is preferable that the aromatic polysulfone is polysulfone, polyphenylsulfone, or polyethersulfone.
[0071]
　Further, in the method for continuously producing an aromatic polyether according to the present embodiment, when the aromatic polyether is a polyaryletherketone, the raw material contains an aromatic dihalogen compound and an aromatic dihydroxy compound, and the alkali metal. It is preferable to mix the compound and the aromatic dihydroxy compound with water and supply them as the aqueous mixture.
[0072]
　Further, in the method for continuously producing aromatic polyether according to the present embodiment, the continuous production apparatus includes a storage chamber for accommodating a plurality of reaction tanks, the reaction tanks are sequentially connected, and the reaction tank is the storage chamber. It is preferable that they communicate with each other through the gas phase in.
[0073]
　Examples are shown below, and embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following embodiments, and it goes without saying that various aspects are possible for details. Further, the present invention is not limited to the above-described embodiment, and various modifications can be made within the scope of the claims, and the present invention also relates to an embodiment obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. In addition, all of the documents described in this specification are incorporated by reference.
Example
[0074]
　[Example 1] Production of PEEK
　A continuous production apparatus having six reaction tanks formed by partitioning a storage chamber by five partition walls is used as shown in FIG. 1 of International Publication No. 2018/159220. The polymerization reaction was carried out. This continuous manufacturing device is a SUS reaction device having a semicircular partition wall and dimensions of an inner diameter of 108 mm and a length of 300 mm.
[0075]
　950 g of N-methyl-2-pyrrolidone (NMP) was charged into this continuous production apparatus. Then, while flowing nitrogen gas from the downstream side of the fifth partition wall from the upstream side at a flow rate of 0.1 NL / min, the first partition wall and the second partition wall from the upstream side are provided by an external heater installed at the bottom of the accommodation chamber 2. The part separated by the partition, that is, the temperature 1 of the second reaction tank from the upstream side is 230 ° C, the temperature 2 of the fifth reaction tank from the upstream side is 260 ° C, and the temperature 2 of the sixth reaction tank from the upstream side. The temperature of 3 was maintained at 260 ° C. In the steady state, the temperature 4 of the first reaction tank from the upstream side was 190 ° C., and the temperature 5 of the fourth reaction tank from the upstream side was 255 ° C. A solution of NMP and 4,4'-difluorobenzophenone (DFBP) at 5.3 g / min and an aqueous solution of water, hydroquinone (HQ) and sodium carbonate at 9.2 g / min, from separate supply lines. It was continuously supplied for 6 hours using a metering pump. The ratio of the components in each solution is NMP: DFBP (weight ratio) = 1068.96: 213.40, DFBP: HQ (molar ratio) = 1.01: 1, HQ: sodium carbonate (molar ratio) = 1: 1. 1. Water: HQ (weight ratio) = 1975.65: 106.62.
[0076]
　At the same time, using a distillation device connected to the continuous manufacturing device, the pressure is controlled to a gauge pressure of 0.3 MPa by the pressure control valve, and the water contained in the raw material and the water generated by the reaction are continuously manufactured. Removed from the device. In addition, the carbon dioxide gas produced by the reaction was released into the atmosphere via a distillation apparatus and a water tank.
[0077]
　Further, the reaction was carried out by supplying NMP at 260 ° C. from the lower part of the sixth reaction tank at a flow rate of 6.0 g / min and diluting the reaction mixture ((DFBP + HQ) / (NMP + DFBP + HQ) = 10% by mass). The mixture was recovered in slurry form.
[0078]
　When the inside of the continuous manufacturing equipment was observed after the operation was completed, no blockage was found in the piping of the continuous equipment, and the presence of the reaction liquid up to the overflow level of the bulkhead was confirmed in all the reaction tanks.
[0079]
　PEEK, which is a reaction product, was collected and analyzed from the reaction mixture recovery line and each reaction vessel. The reaction mixture was added dropwise to 5 times the amount of water to precipitate the reaction product, and the mixture was filtered. Further, it was washed with methanol and then filtered. The obtained cake was dried under vacuum at 60 ° C. for 8 hours to obtain PEEK powder. The weight average molecular weight of this PEEK powder was measured using a gel permeation chromatograph (GPC) GPC-104 of Shodex under the above-mentioned conditions. The PEEK powder collected from the reaction mixture recovery line is 65,000, the PEEK powder collected from the third reaction tank is 12,000, and the PEEK powder collected from the fourth reaction tank is 24,000. The PEEK powder collected from the 5th reaction tank was 42,000, and the PEEK powder collected from the 6th reaction tank was 62,000. The pH of the reaction solution in each reaction tank was measured at 23 ° C. using a pH meter SK-640PH manufactured by Sato Keiki Seisakusho. The reaction tank was 9.8, the sixth reaction tank was 9.0, and the reaction mixture collected from the reaction mixture recovery line was 9.7. The weight average molecular weight was determined by the above method.
[0080] [0080]
　[Example 2] Production of PPSU
　950 g of N-methyl-2-pyrrolidone (NMP) was charged into a continuous production apparatus similar to the apparatus used in Example 1. While flowing nitrogen gas from the downstream side of the fifth partition from the upstream side at a flow rate of 0.1 NL / min, the external heater installed at the bottom of the accommodation chamber 2 allows the first partition and the second partition from the upstream side to flow nitrogen gas. The separated portion, that is, the temperature 1 of the second reaction tank from the upstream side is 210 ° C, the temperature 2 of the fifth reaction tank from the upstream side is 230 ° C, and the temperature 3 of the sixth reaction tank from the upstream side. Was kept at 230 ° C. In the steady state, the temperature 4 of the first reaction tank from the upstream side was 170 ° C., and the temperature 5 of the fourth reaction tank from the upstream side was 225 ° C. A solution of NMP and 4,4'-dichlorodiphenyl sulfone (DCDPS) at 2.2 g / min and an aqueous solution of water, NMP, 4,4'-biphenol, sodium hydroxide and sodium carbonate at 6.5 g / min. Then, it was continuously supplied for 7 hours from different supply lines using a metering pump. The ratio of components in each solution is NMP: DCDPS (weight ratio) = 352.48: 201.01, DCDPS: 4,4'-biphenol (molar ratio) = 1.01: 1, 4,4'-biphenol: water. Sodium oxide: sodium carbonate (molar ratio) = 1: 1.8: 0.15, water: NMP: 4,4'-biphenol (weight ratio) = 1025.90: 407.74: 129.06.
[0081]
　At the same time, using a distillation device connected to the continuous manufacturing device, the pressure is controlled to a gauge pressure of 0.12 MPa by the pressure control valve, and the water contained in the raw material and the water generated by the reaction are continuously manufactured. Removed from the device. In addition, the carbon dioxide gas produced by the reaction was released into the atmosphere via a distillation apparatus and a water tank.
[0082]
　Further, NMP at 210 ° C. was supplied from the lower part of the sixth reaction tank at a flow rate of 6.9 g / min to dilute the reaction mixture ((DCDPS + 4,4'-biphenol) / (NMP + DCDPS + 4,4'-biphenol) =. (Equivalent to 10% by mass) and recovered.
[0083]
　Reactions were collected from the reaction mixture recovery line and analyzed. The reaction mixture was added dropwise to 5 times the amount of water to precipitate the product, and the product was filtered. Then, the cake was further washed and filtered with methanol, and the obtained cake was dried at 60 ° C. for 8 hours under vacuum to obtain PPSU powder. Obtained. The polystyrene-equivalent weight average molecular weight Mw of this PPSU powder by GPC was 36,000. 10,000 PPSU powders collected from the 3rd reaction tank, 20,000 PPSU powders collected from the 4th reaction tank, 37,000 PPSU powders collected from the 5th reaction tank , The amount of PPSU powder collected from the 6th reaction vessel was 39,000. The pH of the reaction solution in each reaction tank was measured at 23 ° C. using a pH meter SK-640PH manufactured by Sato Keiki Seisakusho. The reaction tank was 10.3, the sixth reaction tank was 9.6, and the reaction mixture collected from the reaction mixture recovery line was 7.8.
[0084]
　[Example 3] Production of PES
　950 g of N-methyl-2-pyrrolidone (NMP) was charged into a continuous production apparatus similar to the apparatus used in Example 1. While flowing nitrogen gas from the downstream side of the fifth partition from the upstream side at a flow rate of 0.1 NL / min, the external heater installed at the bottom of the accommodation chamber 2 allows the second partition and the third partition from the upstream side to flow nitrogen gas. The separated portion, that is, the temperature 1 of the third reaction tank from the upstream side is 200 ° C, the temperature 2 of the fifth reaction tank from the upstream side is 220 ° C, and the temperature 3 of the sixth reaction tank from the upstream side. Was kept at 220 ° C. In the steady state, the temperature 4 of the first reaction tank from the upstream side was 150 ° C., and the temperature 5 of the fourth reaction tank from the upstream side was 215 ° C. A solution of NMP and 4,4'-dichlorodiphenyl sulfone (DCDPS) at 3.5 g / min and an aqueous solution of water, 4,4'-dihydroxydiphenyl sulfone (bisphenol S) and sodium hydroxide at 6.4 g / min. In min, it was continuously supplied for 11 hours from different supply lines using a metering pump. The ratio of components in each solution is NMP: DCDPS (weight ratio) = 760.22: 201.01, DCDPS: bisphenol S (molar ratio) = 1: 1, bisphenol S: sodium hydroxide (molar ratio) = 1: 2. Water: bisphenol S (weight ratio) = 1547.23: 175.19.
[0085]
　At the same time, using a distillation device connected to the continuous manufacturing device, the pressure is controlled to a gauge pressure of 0.1 MPa by the pressure control valve, and the water contained in the raw material and the water produced by the reaction are continuously manufactured. Removed from the device. In addition, the carbon dioxide gas produced by the reaction was released into the atmosphere via a distillation apparatus and a water tank.
[0086]
　Reactions were collected from the reaction mixture recovery line and analyzed. The reaction mixture was added dropwise to 5 times the amount of water to precipitate the product, and the product was filtered. Then, the cake was further washed and filtered with methanol, and the obtained cake was dried at 60 ° C. for 8 hours under vacuum to obtain PES powder. Obtained. The polystyrene-equivalent weight average molecular weight Mw of this PES powder by GPC was 14,000. The PES powder collected from the third reaction tank is 5,000, the PES powder collected from the fourth reaction tank is 5,000, and the PES powder collected from the fifth reaction tank is 6,000. , The PES powder collected from the 6th reaction tank was 14,000. The pH of the reaction solution in each reaction tank was measured at 23 ° C. using a pH meter SK-640PH manufactured by Sato Keiki Seisakusho, and the third reaction tank was 11.0 and the fourth reaction tank was 11. 1. The 5th reaction tank was 11.0, the 6th reaction tank was 10.1, and the reaction mixture collected from the reaction mixture recovery line was 10.2.
[0087]
　[Example 4] Production of PPSU
　950 g of N-methyl-2-pyrrolidone (NMP) was charged into a continuous production apparatus similar to the apparatus used in Example 1. While flowing nitrogen gas from the downstream side of the fifth partition from the upstream side at a flow rate of 0.1 NL / min, the external heater installed at the bottom of the accommodation chamber 2 allows the second partition and the third partition from the upstream side to flow nitrogen gas. The separated portion, that is, the temperature 1 of the third reaction tank from the upstream side is 200 ° C, the temperature 2 of the fifth reaction tank from the upstream side is 210 ° C, and the temperature 3 of the sixth reaction tank from the upstream side. Was kept at 210 ° C. In the steady state, the temperature 4 of the first reaction tank from the upstream side is 170 ° C, the temperature 5 of the second reaction tank from the upstream side is 190 ° C, and the temperature 6 of the fourth reaction tank from the upstream side is 205 ° C. It was ° C. A solution of NMP with 4,4'-dichlorodiphenyl sulfone (DCDPS) and 4,4'-biphenol at 4.3 g / min and an aqueous solution of water, sodium hydroxide and sodium carbonate at 1.2 g / min. It was continuously supplied for 7 hours from different supply lines using a metering pump. The ratio of the components in each solution is NMP: DCDPS: 4,4'-biphenol (weight ratio) = 760.22: 129.06: 201.01, DCDPS: 4,4'-biphenol (molar ratio) = 1.01. 1,4,4'-biphenol: sodium hydroxide: sodium carbonate (molar ratio) = 1: 1.8: 0.15, water: sodium hydroxide: sodium carbonate (weight ratio) = 243.69: 49. It was 90: 11.02.
[0088]
　At the same time, using a distillation device connected to the continuous manufacturing device, the pressure is controlled to a gauge pressure of 0.06 MPa by the pressure control valve, and the water contained in the raw material and the water generated by the reaction are continuously manufactured. Removed from the device. In addition, the carbon dioxide gas produced by the reaction was released into the atmosphere via a distillation apparatus and a water tank.
[0089]
　Further, NMP at 210 ° C. was supplied from the lower part of the sixth reaction tank at a flow rate of 6.9 g / min to dilute the reaction mixture ((DCDPS + 4,4'-biphenol) / (NMP + DCDPS + 4,4'-biphenol) =. (Equivalent to 10% by mass) and recovered.
[0090]
　Reactions were collected from the reaction mixture recovery line and analyzed. The reaction mixture was added dropwise to 5 times the amount of water to precipitate the product, and the product was filtered. Then, the cake was further washed and filtered with methanol, and the obtained cake was dried at 60 ° C. for 8 hours under vacuum to obtain PPSU powder. Obtained. The polystyrene-equivalent weight average molecular weight Mw of this PPSU powder by GPC was 11,000. The PPSU powder collected from the 3rd reaction tank is 7,000, the PPSU powder collected from the 4th reaction tank is 10,000, and the PPSU powder collected from the 5th reaction tank is 13,000. The amount of PPSU powder collected from the 6th reaction vessel was 14,000. The pH of the reaction solution in each reaction tank was measured at 23 ° C. using a pH meter SK-640PH manufactured by Sato Keiki Seisakusho. The reaction tank was 10.5, the sixth reaction tank was 10.0, and the reaction mixture collected from the reaction mixture recovery line was 10.0.
[0091]
　[Comparative Example 1] Production of PEEK
　950 g of N-methyl-2-pyrrolidone (NMP) was charged into a continuous production apparatus similar to the apparatus used in Example 1. While flowing nitrogen gas from the downstream side of the fifth partition from the upstream side at a flow rate of 0.1 NL / min, the external heater installed at the bottom of the accommodation chamber 2 allows the first partition and the second partition from the upstream side to flow nitrogen gas. The separated portion, that is, the temperature 1 of the second reaction tank from the upstream side is 230 ° C, the temperature 2 of the fifth reaction tank from the upstream side is 260 ° C, and the temperature 3 of the sixth reaction tank from the upstream side. Was kept at 260 ° C. In the steady state, the temperature 4 of the first reaction tank from the upstream side was 190 ° C., and the temperature 5 of the fourth reaction tank from the upstream side was 255 ° C. The part separated by the second partition, that is, the temperature 1 of the second reaction tank from the upstream side is set to 220 ° C., and the part separated by the third partition and the fourth partition, that is, the second from the upstream side. The temperature 2 of the 4th reaction tank is set to 260 ° C., and the temperature 3 of the 6th reaction tank from the upstream side is set to 260 ° C. Retained. Using a metering pump from each supply line, NMP, 4,4'-difluorobenzophenone (DFBP), hydroquinone (HQ), and potassium carbonate are combined into one dispersion, that is, from one raw material supply line 6 .4 g / min (NMP: DFBP (weight ratio) = 711.30: 142.00, DFBP: HQ (molar ratio) = 1.01: 1, HQ: potassium carbonate (molar ratio) = 1: 1.1) The raw materials were continuously supplied while stirring with a stirrer at the flow rate of.
[0092]
　Potassium carbonate having an average particle diameter of 95 μm or more in the solution was pulverized into a slurry at about 10,000 rpm / min using a homogenizer before supply (average particle diameter of 95 μm or less).
[0093]
　At the same time, using a distillation apparatus connected to the continuous production apparatus, water produced by the reaction was continuously removed from the continuous production apparatus while controlling the pressure to a gauge pressure of 0.3 MPa by a pressure regulating valve. In addition, the carbon dioxide gas produced by the reaction was released into the atmosphere via a distillation apparatus and a water tank.
[0094]
　Further, NMP at 260 ° C. was supplied from the lower part of the sixth reaction tank at a flow rate of 6.0 g / min to dilute the reaction mixture ((DFBP + HQ) / (DFBP + HQ + NMP) = 10% by mass).
[0095]
　Fifteen minutes after the start of supply, a blockage occurred in the supply line. Even after the blockage was cleared, the blockage occurred intermittently 5 to 30 minutes after the resumption of supply, and the operation could not be continued. Almost no reaction mixture was produced due to occlusion 15 minutes after the start of feeding.
The scope of the claims
[Claim 1]

　By performing a polymerization reaction in the polymerization solvent in 　a supply step of supplying a polymerization solvent, an alkali metal compound and a raw material into a continuous production apparatus in which a plurality of reaction tanks are sequentially connected, and in at least one of the reaction tanks. , A polymerization step of forming a reaction mixture and
　a moving step of sequentially moving the reaction mixture to each reaction vessel are performed in parallel, and the
　alkali metal compound is supplied as an aqueous mixture, continuously producing an aromatic polyether. Method.
[Claim 2]
　The continuous production method according to claim 1, wherein the aqueous mixture containing at least the alkali metal compound is supplied into the continuous production apparatus separately from the mixture composed of at least a part of the raw materials and the polymerization solvent.
[Claim 3]
　The continuous production method according to claim 1 or 2, wherein the raw material is in the form of a solution in which the raw material is dissolved in the polymerization solvent.
[Claim 4]
　The continuous production method according to any one of claims 1 to 3, wherein the pH of the reaction mixture in at least one or more reaction tanks is 9 or more and 12.5 or less.
[Claim 5]
　In at least one reaction vessel, the reaction mixture comprises the aromatic polyether having a weight average molecular weight of 2,000 or more and 50,000 or less, and the pH of the reaction mixture in at least one of the at least one reaction vessel. The continuous production method according to any one of claims 1 to 4, wherein is 9 or more and 12.5 or less.
[Claim 6]
　The continuous production method according to any one of claims 1 to 5, which comprises an aromatic dihalogen compound and an aromatic dihydroxy compound as the raw material.
[Claim 7]
　The continuous production method according to any one of claims 1 to 6, wherein the alkali metal compound contains an alkali metal carbonate.
[Claim 8]
　The continuous production method according to any one of claims 1 to 7, wherein the aromatic polyether is a polyaryletherketone.
[Claim 9]
　The continuous production method according to claim 8, wherein the polyaryletherketone is a polyetheretherketone.
[Claim 10]
　The continuous production method according to any one of claims 1 to 7, wherein the aromatic polyether is aromatic polysulfone.
[Claim 11]
　The continuous production method according to claim 10, wherein the aromatic polysulfone is polysulfone, polyphenylsulfone, or polyethersulfone.
[Claim 12]
　The continuous production method according to claim 8 or 9, wherein the raw material contains an aromatic dihalogen compound and an aromatic dihydroxy compound, and the alkali metal compound and the aromatic dihydroxy compound are mixed with water and supplied as the aqueous mixture. ..
[Claim 13]
　The continuous manufacturing apparatus includes a storage chamber for accommodating a plurality of reaction tanks, the
　reaction tanks are sequentially connected, and the
　reaction tanks communicate with each other via a gas phase in the storage chambers. The continuous manufacturing method according to any one of 12.