JP2010018763A - Method of manufacturing desalination polycondensation based polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a desallination polycondensation based polymer in which a desallination polycondensation reaction is stably and effectively performed, thereby a polymer having a desired a molecular weight can be easily obtained and a purification process after the end of the desallination polycondensation reaction is simply performed in a shorter time. <P>SOLUTION: The method of manufacturing a desallination polycondensation based polymer includes a process in which a desallination polycondensation reaction is performed using an alkaline metal salt catalyst and/or an alkaline-earth metal salt catalyst, wherein the desallination polycondensation reaction process uses a powder which has a specific surface of 0.8 m<SP>2</SP>/g and in which an amount passing through a sieve of 45 μm mesh is 20% by mass in a particle size measurement by a sieve method as an alkaline metal salt catalyst and/or an alkaline-earth metal salt catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a method for producing a desalted polycondensation polymer. More specifically, the present invention relates to a method for producing a desalted polycondensation polymer suitably used for producing a fluorine polymer produced by an industrial production facility.

As one of the methods for producing a polymer, polycondensation in which reactive functional groups in a monomer are polymerized by condensation reaction is known, and as one of them, a basic metal salt is used as a catalyst. Desalination polycondensation in which polycondensation is performed while desalting is industrially performed.
Examples of the desalting polycondensation reaction include ether polymers and sulfide polymers in which hydrogen halide is eliminated from a compound having two or more halogen elements as substituents and a compound having two or more hydroxyl groups or thiol groups. The reaction etc. which produce | generate are mentioned. The detached hydrogen halide reacts with the basic metal salt, and a by-product salt is deposited. It is well known that engineer plastics such as polyether ketone and polyether sulfone can be obtained from these reactions. Furthermore, fluorine-containing aryl ether polymers containing fluorine in an aromatic group are compounds having excellent heat resistance, electrical characteristics, and optical characteristics, and therefore, such as high-frequency wiring boards and multilayer wiring boards. It is known as an optical film material for use in materials, display substrates such as liquid crystal display elements, and display devices.

In the production of a fluorinated aryl ether ketone polymer using such a desalting polycondensation reaction, it is disclosed that the production is carried out by polycondensing monomers in an organic solvent using a basic compound as a catalyst ( For example, see Patent Document 1). In addition, when a polyaryl ether is produced by polycondensation of a dihalogenodiphenyl compound and a dihydric phenol compound in an organic solvent for the purpose of producing a polymer with good reproducibility and in a short time, the specific surface area is 0. A method of using alkali metal compound particles having a particle size of 3 m ² / g or more as a catalyst and a method of using particles having a bulk density of 1.3 g / cc or less as an alkali metal compound as a catalyst are disclosed (for example, (See Patent Documents 2 and 3). As described above, when a polyaryl ether is produced using a basic metal salt as a catalyst, a method using a finely divided basic metal salt of a catalyst is known in order to facilitate the production. However, when a finely divided basic metal salt is used, it may take a long time when filtration is performed as a purification step for removing the basic metal salt after the reaction.

In addition, purification of the product after the desalting polycondensation reaction is also performed by extraction. In the case of producing a polymer using the desalting polycondensation reaction, a nonpolar solvent is added after the desalting polycondensation reaction. And a method for extracting the produced polymer is disclosed (for example, see Patent Document 4), but it is inefficient to remove the precipitated by-product by dissolving it again in water. As described above, in the method for producing a desalted polycondensation polymer using a desalted polycondensation reaction, although technical improvements have been advanced from the viewpoint of increasing reaction efficiency and purification purity, The basic metal salt catalyst used in the reaction and the by-product salt produced by the desalting polycondensation reaction have not necessarily been sufficiently improved with respect to removing the reaction product in a short time without going through complicated steps. However, in actual production, the removal of the basic metal salt catalyst and by-product salt in the purification process of the product polymer can be a rate-limiting step in the production of the polymer. Therefore, while producing a polymer with high reaction efficiency, it is possible to remove a basic metal salt used as a catalyst in a shorter time and more easily and to make the purification process of the polymer more efficient. There was room for ingenuity.
JP 2001-64226 A (page 1-2) JP-A-6-32895 (page 1-2) JP-A-6-32894 (page 1-2) JP 2007-119756 A (page 1-2)

The present invention has been made in view of the above-described present situation, and can stably and efficiently carry out a desalting polycondensation reaction to easily obtain a polymer having a desired molecular weight. It aims at providing the manufacturing method of the desalinization polycondensation type polymer which can perform the refinement | purification process after reaction easily in a short time.

In the case of producing a polymer using a desalting polycondensation reaction, the present inventors can perform the desalting polycondensation reaction stably and efficiently, and used the polymer to be produced as a catalyst. Various studies were made on a method for producing a desalted polycondensation polymer so that the purification step for separating the basic metal salt can be easily performed in a short time.
Therefore, in order to increase the reaction efficiency of the desalting polycondensation reaction, it is necessary to increase the specific surface area of the basic metal salt in order to increase the catalytic ability of the basic metal salt and shorten the reaction time. First, I paid attention to it.
On the other hand, when these basic metal salts are used in a fine powder form in order to increase the specific surface area, when the step of removing the basic metal salt is performed by filtration, a fine powder of the basic metal salt is generated. It has been found that a membrane-like substance is formed on the filtration membrane by the polymer, and the filtration membrane is covered with this membrane-like substance, so that the filtration efficiency is remarkably lowered and the productivity is hindered. This is because the polymer produced acts as a binder between fine particles, and when the particles are fine, a phenomenon such as agglomeration occurs, sticking on the filtration membrane, forming a membrane and clogging. It is considered a thing. In such a case, it can be considered that the filter is usually replaced. However, in this reaction, a large amount of salt such as by-products is formed, and a cake layer is formed on the filter. Therefore, unlike normal filter replacement, it is very complicated and unrealistic. In addition, it is conceivable that the filtration area is increased and clogging is less likely to occur, but this is not possible in a normal industrial manufacturing process. In addition, it is possible to place several filters in parallel and move to a new filter when the clogging starts and the filtration speed slows down, but this is not industrially preferable. It is preferable to carry out with a vessel.
Therefore, in order to achieve both the reaction efficiency in the desalting polycondensation reaction and the removal efficiency of the basic metal salt, and to achieve the problem of industrially high production efficiency and a useful production method, the form of the basic metal salt particles is changed. As a result of various investigations, a technique has been found in which the specific surface area is more than a certain value and the particle diameter is specified.
As a result, the reaction can be carried out stably and efficiently, and a membrane formed on the filtration membrane by the polymer and basic metal salt particles when filtration is performed as a purification step for the produced polymer. Since it is not covered with the particulate matter, the filtration efficiency is not greatly impaired, and as a result, the polymer purification step can be performed in a short time and simply. This is because the use of basic metal salt particles having an average particle diameter greater than a specific value makes it difficult for the produced polymer to be embedded between the particles and to pass through, in other words, the basic metal salt particles are filter aids. It is thought that the particles themselves act as a coarse filter.
As described above, in the method for producing a polymer using the desalting polycondensation reaction, it was found that the above-mentioned problems can be solved brilliantly by using those identified as basic metal salt particles, and the present invention has been achieved. Is.

That is, the present invention is a method for producing a desalted polycondensation polymer comprising a step of performing a desalting polycondensation reaction using an alkali metal salt catalyst and / or an alkaline earth metal salt catalyst. In the reaction step, the amount of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst that passes through a sieve having a specific surface area of 0.8 m ² / g or more and having a mesh size of 45 μm as measured by a sieve method. Is a method for producing a desalted polycondensation polymer using a powdery substance having a content of 20% by mass or less.
The present invention is described in detail below.

The method for producing a polymer by a desalting polycondensation reaction of the present invention is a method in which a desalting polycondensation reaction is performed using an alkali metal salt catalyst and / or an alkaline earth metal salt catalyst. Is a reaction between monomers having two or more functional groups, and in the reaction between the functional group of one monomer and the functional group of another monomer, the acid is eliminated. The reaction in which a new bond is formed between the functional groups continuously occurs to form a polymer. The detached acid reacts with an alkali metal salt catalyst and / or an alkaline earth metal salt catalyst to produce a by-product salt. Examples of the reaction for producing a polymer by a desalting polycondensation reaction include, for example, an ether system in which hydrogen halide is eliminated from a compound having two or more halogen elements as a substituent and a compound having two or more hydroxyl groups. The reaction etc. which a polymer produces | generates are mentioned. The monomer used for the desalting polycondensation reaction may be one type or two or more types.
The method for producing a polymer of the present invention includes a step of performing a desalting polycondensation reaction and a step of removing the alkali metal salt catalyst and / or the alkaline earth metal salt catalyst after the desalting polycondensation reaction. Other steps may be included.

The alkali metal salt catalyst and / or alkaline earth metal salt catalyst used in the method for producing a polymer of the present invention acts to promote the desalting polycondensation reaction by collecting the acid produced by the desalting polycondensation reaction. It is preferable that it has. Examples of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst having such an action include potassium carbonate, lithium carbonate, potassium hydroxide, and potassium fluoride. One or more of these may be used. Can be used. Among these, it is preferable to use potassium carbonate.

The amount of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst used in the method for producing a polymer by the desalting polycondensation reaction of the present invention is 0 with respect to the reactive functional group of the monomer component. .8 to 4 equivalents are preferred. More preferably, it is 0.9-3.0 equivalent. More preferably, it is 1.0-2.0 equivalent. Thereby, it is possible to prevent the desalting polycondensation reaction from proceeding abruptly, and it is excellent in effects such as being able to easily obtain a polymer having a desired molecular weight.

The reactive functional group possessed by the monomer component is a functional group possessed by a monomer used as a raw material for the desalting polycondensation reaction, and is crosslinked by an alkali metal salt catalyst and / or an alkaline earth metal salt catalyst. It means a nucleophilic species that causes a reaction. The reactive functional group is preferably either a hydroxyl group or a thiol group. More preferably, it is a hydroxyl group.
The use of 0.8 to 4 equivalents of catalyst with respect to the reactive functional group of the monomer component means that, for example, when potassium carbonate is used as the catalyst, potassium carbonate has two potassium ions. The use of 0.8 to 4 moles of potassium carbonate per mole of functional monomer (for example, bisphenol).

The specific surface area of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst used in the method for producing a polymer by the desalting polycondensation reaction of the present invention is 0.8 m ² / g or more. By using one having a specific surface area of 0.8 m ² / g or more, the desalting polycondensation reaction can be performed with high efficiency. The specific surface area of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst is preferably 1.0 m ² / g or more. More preferably, it is 1.2 m ² / g or more. By using an alkali metal salt catalyst and / or alkaline earth metal salt catalyst having a larger specific surface area, the chance of contact between the catalyst and the reaction raw material is further increased, and the desalting polycondensation reaction is performed with higher efficiency. Is possible. When the specific surface area is smaller than 0.8 m ² / g, the desalting polycondensation reaction cannot be performed with sufficiently high efficiency unless the amount of the catalyst is increased. However, when the amount of the catalyst is increased, the catalyst is used in the purification process. It is not preferable because it takes a long time to remove.
The specific surface area can be measured using a method generally referred to as a BET method. The metal salt used as a catalyst can be obtained by drying at a temperature under vacuum and measuring the nitrogen adsorption amount.

The size of the particles of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst used in the method for producing a polymer by the desalting polycondensation reaction of the present invention passes through a sieve having a mesh size of 45 μm as measured by a sieve method. The amount to be processed is 20% by mass or less. When fine powder is used as a catalyst, when filtration is performed in the purification step, the produced polymer adheres to the fine powder particle surface of the catalyst or the like and binds the particles to form a tight film product.
Filtration is hindered by covering the membrane with this membrane-like product, and it takes a very long time for filtration or becomes clogged. On the other hand, when the catalyst particles are larger than a certain size, the gaps between the particles are large, and a tight film cannot be formed only with the polymer that is in close contact with the catalyst particle surface. Play a role. Therefore, it can filter without clogging. If the amount passing through a sieve with a mesh opening of 45 μm is 20% by mass or less, the formed film-like product is not sufficiently tightened and can be filtered efficiently. It becomes.
As the size of the particles of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst, those having an amount of passing through a sieve having an opening of 45 μm by particle size measurement by a sieving method are preferably 10% by mass or less. Preferably, it is 7 mass% or less. More preferably, it is 5 mass% or less. More preferably, it is 1 mass% or less.

As a method for producing an alkali metal salt catalyst and / or alkaline earth metal salt catalyst used in the method for producing a polymer by a desalting polycondensation reaction of the present invention, potassium hydroxide and carbon dioxide are reacted to obtain potassium hydrogen carbonate. A method of synthesizing potassium carbonate and heating the synthesized potassium hydrogen carbonate to synthesize potassium carbonate is preferable. The potassium carbonate obtained by the production method has a porous particle shape as compared with potassium carbonate obtained by a production method in which potassium hydroxide and carbon dioxide are reacted to directly synthesize potassium carbonate. As a result, it is possible to obtain potassium carbonate particles having a large specific surface area and a large pore volume.

In the method for producing a polymer in the desalting polycondensation reaction of the present invention, it is common to perform a filtration step as a purification step for separating the produced polymer from the basic metal salt and by-product salt used as a catalyst. . It is possible to perform direct extraction or separation by reprecipitation, but considering the waste liquid, it is reasonable to remove the precipitated salts as they are. Although the magnitude | size of a filter can be selected arbitrarily, it is preferable to select the filter so that the cake thickness deposited on a filtration surface may be 25 cm or less.

The polymer produced in the method for producing a polymer by the desalting polycondensation reaction of the present invention preferably has a weight average molecular weight of 10,000 or more. When the polymer produced has a weight average molecular weight of 10,000 or more, it can be produced as a finely divided alkali metal salt catalyst and / or alkaline earth metal salt catalyst by filtration as a purification step after the desalting polycondensation reaction. The formation of a film-like substance with the polymer is more noticeable. Therefore, when producing a polymer having a weight average molecular weight of 10,000 or more, the effect of the production method of the present invention is more remarkably exhibited. Further, if the molecular weight is not high to some extent, the performance as a film or a molded product may not be sufficient in applications using a polymer.
The weight average molecular weight is more preferably 20000 or more. In this case, the performance of the polymer as a self-supporting film is further improved, which is advantageous in terms of performance such as flexibility and crack resistance.
Moreover, since the viscosity of a polymer solution will become high and handling will become difficult when a weight average molecular weight exceeds 300000, it is preferable that the weight average molecular weight of the polymer manufactured is 300000 or less. More preferably, it is 200000 or less.
In addition, when performing a desalination polycondensation reaction using the particle | grains of a basic metal salt like this invention, it is difficult to set it as the weight average molecular weight of 5000 or less.
The said weight average molecular weight can be measured by the gel permeation chromatography (GPC apparatus, developing solvent; tetrahydrofuran) by polystyrene conversion. As other measurement conditions such as the column used, it is preferable to use those used in the examples and comparative examples of the present specification.

The monomer used as a raw material in the method for producing a polymer by the desalting polycondensation reaction of the present invention is not particularly limited as long as it is a raw material for the desalting polycondensation reaction, and is a halogen atom, a hydroxyl group, or a thiol group. , One selected from monomers having two or more substituents such as a mercapto group and an amino group, which undergoes a desalting polycondensation reaction, or a combination of two or more types Can do. Examples of a monomer that undergoes a desalting polycondensation reaction with only one type of monomer include, for example, a compound having both a halogen element and a hydroxyl group as substituents in one molecule, and a halogen element in one molecule. Examples thereof include compounds having both a thiol group as a substituent. These compounds may be used alone or in combination of two or more. Examples of combinations of two or more monomers having two or more identical substituents in one molecule include compounds having two or more halogen elements such as bromine, chlorine and fluorine and two or more hydroxyl groups. And a combination of a compound having two or more halogen elements and a compound having two or more thiol groups.
The polymer obtained by the production of the polymer of the present invention is such that at least a part of the polymer chain of the obtained polymer is formed by a desalting polycondensation reaction, and the other part of the polymer chain is desorbed. It may be formed by a reaction other than the salt polycondensation reaction. That is, the monomer used as a raw material in the method for producing a polymer of the present invention may contain other monomers as long as it contains a monomer that forms a polymer chain by a desalting polycondensation reaction. .

Examples of the monomer that undergoes the desalting polycondensation reaction with only one kind of the monomer include 4-hydroxy-4 ′-(2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (HPDE) and the like. Examples thereof include compounds having both a halogen element and a hydroxyl group as substituents in one molecule. As a monomer used in the case of carrying out a desalting polycondensation reaction by combining monomers having two or more identical substituents in one molecule, 9,9-bis (4-hydroxyphenyl) fluorene (BPF) ), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (Bis-AF), 2,2- (4-hydroxyphenyl) propane (BisA), etc. A compound having two or more hydroxyl groups, such as bisphenols of 4,4'-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (BPDE), 4-phenoxy-2,3,5, 6-tetrafluorobenzonitrile (PTFBN), 4,4′-bis (2,3,4,5,6-pentafluorobenzoyloxy) diphenyl ether (BPDEs), 2,2- Scan compound having two or more halogen atoms, such as (pentafluoro-benzyloxy phenyl) -1,1,3,3-hexafluoropropane (BP6FBA), and the like.
For example, when performing a desalination polycondensation reaction by combining monomers having two or more identical substituents in one molecule, from the viewpoint of effective use of the monomer, The other monomer is preferably used in a ratio of 0.8 to 1.2 mol. More preferably, it is used in a ratio of 0.9 to 1.1 mol of another monomer per 1 mol of one monomer.

The polymer produced in the method for producing a polymer by the desalting polycondensation reaction of the present invention comprises polyethersulfone, polyetherketone, polyetheretherketone, polyethernitrile, polyetheramide, and polyetherester. It is preferably at least one selected from the group.
In addition, the said polyether sulfone should just be a compound which has at least one ether bond and a sulfonic acid group in a molecule | numerator, and the ratio of an ether bond and a sulfonic acid group is not restrict | limited in particular. Similarly for the above polyether ketone, polyether nitrile, polyether amide, and polyether ester, the ratio of ether bond to ketone group in the molecule, the ratio of ether bond to nitrile group, ether bond and amide group The ratio of and the ratio of ether bond to ester bond are not particularly limited.
Moreover, it is preferable that the polymer manufactured in the manufacturing method of the polymer by the desalting polycondensation reaction of this invention is a fluorine-containing polymer. A fluorine-containing polymer is a polymer in which a fluorine atom is essential.

Furthermore, the polymer produced in the method for producing a polymer by the desalting polycondensation reaction of the present invention is preferably a fluorine-containing aromatic polymer. The fluorine-containing aromatic polymer is a polymer having an aromatic ring, and a polymer in which a fluorine atom is essential.
Therefore, the polymer produced in the method for producing a polymer by the desalting polycondensation reaction of the present invention includes polyethersulfone, polyetherketone, polyetheretherketone, At least one selected from the group consisting of ether nitriles, polyether amides, and polyether esters is more preferable, and fluorine-containing polyaryl ethers and fluorine-containing polyaryl sulfides are more preferable.
In the method for producing a polymer by a desalting polycondensation reaction of the present invention, a suitable monomer is appropriately selected from the above-mentioned monomers so that these polymers are produced. A polycondensation reaction is preferably performed.

The fluorine-containing polyaryl ether-based polymer is a polymer having a fluorine atom as essential and having an aromatic ring and an ether bond, and the fluorine-containing polyaryl sulfide-based polymer is essential as a fluorine atom, having an aromatic ring and a thiol. There are no particular restrictions on the order of bonding or the position where the fluorine atom is bonded, but the polymer has a fluorine atom in at least one of the aromatic rings in the repeating unit. preferable.

Among the above, the fluorine-containing aromatic polymer of the present invention has the following formula (1);

(Wherein, Z is the same or different and represents a divalent organic group or a direct bond. M is the same or different and represents the number of fluorine atoms added to the aromatic ring, and is an integer of 1 to 4. R ¹ is the same or different and is a divalent organic group, Y is the same or different and represents an oxygen atom or a sulfur atom), and a polymer having a repeating unit having a structure represented by: And / or the following formula (2):

Wherein R ¹ is the same or different and is a divalent organic group. R ² is the same or different and is an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, An alkylamino group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms, which are substituted It is more preferable that the polymer has a repeating unit having a structure represented by:
These repeating units may be the same or different, and when constituted by different repeating units, they may be in any form such as a block shape or a random shape. When the fluorine-containing polyarylether-based polymer has both a repeating unit containing a fluorine-containing polyaryletherketone structure and a repeating unit containing a fluorine-containing polyarylsulfide structure, the constituent ratio of both is not particularly limited.

In the general formula (1), Z represents that a divalent organic group or a benzene ring is directly bonded. The divalent organic group preferably contains a C, S, N and / or O atom. More preferred are divalent organic groups containing a carbonyl group, sulfide group, sulfone group, and heterocyclic ring, and more preferred are the following formulas (3-1) to (3-10). Among these, (3-5) to (3-7) are particularly preferable.

X is a divalent organic group, and is preferably, for example, the following formulas (4-1) to (4-19).

In the above formulas (4-1) to (4-19), as the substituent in Y ¹ , Y ² , Y ³ and Y ⁴ , for example, hydrogen, an alkyl group which may have a substituent, or an alkoxyl group is preferable. It is. More preferred are an alkyl group and an alkoxyl group having 1 to 30 carbon atoms and optionally having a substituent.

X is more preferably the following (5-1) to (5-20), and more preferably (5-6), (5-7), (5-15), and (5-20) below. is there.

In the above formula (1), R ¹ is the same as X above. Note that the fact that R ¹ is the same as X does not mean that R ¹ and X are preferably the same group. R ¹ and the above X may be the same or different.

The molecular weight distribution (Mw / Mn) of the polymer produced in the method for producing a polymer by the desalting polycondensation reaction of the present invention is preferably 5 or less. More preferably, it is 4 or less.

The use of an aprotic polar solvent as the solvent for the desalting polycondensation reaction in the method for producing a polymer by the desalting polycondensation reaction of the present invention is one of the preferred embodiments of the present invention. The aprotic polar solvent is not particularly limited as long as it is a solvent generally classified as an aprotic polar solvent, but it is preferable that the solubility in water is 10% by mass or more. As the aprotic polar solvent having a solubility in water of 10% by mass or more, acetone, methyl ethyl ketone (MEK), cyclohexanone, acetonitrile, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like are preferable. Moreover, what is arbitrarily mixed with water has an influence on the extraction performed after the filtration step, and therefore, 10% by mass or more of a solution that is not arbitrarily mixed with water, such as MEK, is more preferable. . These solvents may be used alone or in combination of two or more.

One of the preferred embodiments of the present invention is to use molecular sieve as a dehydrating agent in the method for producing a polymer by the desalting polycondensation reaction of the present invention. The amount of molecular sieve used is preferably 5 to 50 times the weight of water (same molar equivalent as the monomer) generated in the desalting polycondensation reaction. More preferably, it is 8-30 times weight, More preferably, it is 10-20 times weight.

In the method for producing a polymer by the desalting polycondensation reaction of the present invention, the reaction temperature of the desalting polycondensation reaction is arbitrary. Usually, in the case of a polymer containing no fluorine produced using desalting polycondensation, the reaction temperature in the system is usually carried out at a high temperature of 100 ° C. or higher, or dehydration is carried out using an azeotropic solvent. In contrast, the desalting polycondensation step in the present invention is particularly effective when performed at 100 ° C. or lower. In particular, when producing a fluorine-containing aromatic polymer, the temperature is preferably 0 to 100 ° C. When the reaction temperature is lower than 0 ° C., the reaction is difficult to proceed and the molecular weight is difficult to increase. Moreover, when it exceeds 100 degreeC, there exists a possibility that a polymer may gelatinize. The reaction temperature is preferably 40 to 95 ° C, more preferably 60 to 90 ° C. When it is performed at 100 ° C. or lower, water tends to be present in the system, and a dehydrating agent such as molecular sieve is essential in order to facilitate the reaction.

In the method for producing a polymer by the desalting polycondensation reaction of the present invention, the reaction time of the desalting polycondensation reaction is preferably 2 to 10 hours.
When the reaction time is longer than 10 hours, in an aromatic ring having 5 fluorine atoms such as 4,4'-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether, Since not only fluorine at the position but also fluorine at the 2-position of the benzoyl group is placed in a reactive state, the polymer may be gelled. The reaction time is more preferably 4 to 8 hours.

In the method for producing a polymer by the desalting polycondensation reaction of the present invention, the polymerization concentration is preferably 10% by mass or more. The polymerization concentration is a solid content concentration excluding the catalyst and molecular sieve. If it is lower than this, the polymerization efficiency is poor, and the productivity finally obtained is also low. More preferably, it is 15 mass% or more. In the above production method, by performing the desalting polycondensation reaction with stirring, the residual amount of each monomer component can be reduced even at such a polymerization concentration, and it has a desired molecular weight. A polymer can be obtained.

In the method for producing a polymer by the desalting polycondensation reaction of the present invention, after performing the desalting polycondensation reaction and filtering, performing a step of performing extraction using a nonpolar solvent is a preferred embodiment of the present invention. One. In the use of electronic materials and optical materials, importance is attached to purity, so that sufficient effects can be obtained by performing extraction after filtration. The nonpolar solvent is not particularly limited as long as it is not miscible with water, and one type of solvent may be used, or two or more types may be used. As the nonpolar solvent, for example, ester, aromatic, and ketone are preferable. Moreover, as a nonpolar solvent, the solvent whose boiling point is 150 degrees C or less is preferable among the things mentioned above. When the nonpolar solvent is 150 ° C. or higher, it takes time to completely remove the solvent from the polymer, or solvent replacement becomes difficult. More preferably, the temperature is 130 ° C. or lower, and for example, ethyl acetate, butyl acetate, toluene, methyl isobutyl ketone (MIBK) and the like can be used. More preferred are ethyl acetate, butyl acetate, and MIBK. Most preferably, the boiling point is 90 ° C. or lower.
By selecting a solvent having a low boiling point as the extraction solvent, the solvent can be easily replaced with a solvent having a boiling point higher than that, so that the solvent can be selected. The amount of the nonpolar solvent used for extraction is preferably at least twice that of the polymerization solvent, more preferably at least 3 times.

The method for producing a polymer by a desalting polycondensation reaction of the present invention includes a step of performing desalting polycondensation while stirring a reaction solution containing a monomer component in a polymerization tank equipped with a paddle blade. 1 is one of the preferred embodiments of the present invention.
When the production method of the present invention has the above embodiment, the state in which the alkali metal salt catalyst and / or alkaline earth metal salt catalyst used as the desalting catalyst is dispersed in the polymerization tank is maintained, and the effective catalyst amount is maintained high. As a result, the desalting polycondensation reaction can be performed more efficiently.

In the polymerization tank equipped with the paddle blade, the ratio (α / D) of the clearance (α) between the bottom of the polymerization tank and the bottom end of the paddle blade with respect to the tank diameter (D) is preferably 5% or less.
The ratio (α / D) is preferably 4% or less. More preferably, it is 3% or less, More preferably, it is 2% or less, Most preferably, it is 1% or less.
The paddle blade is a stirring blade having a flat plate portion shape. The clearance means the distance from the lowest end of the paddle blade to the bottom of the polymerization tank in the vertical direction. Moreover, a tank diameter is a diameter inside a polymerization tank.

When the desalination polycondensation is industrially performed using a paddle blade that satisfies the above clearance ratio, for example, the catalyst is less likely to stay at the bottom of the kettle, and the dispersed state of the catalyst in the reaction solution becomes uniform. The phenomenon that the catalyst sticks to the bottom of the kettle due to the polymerization reaction or the like is less likely to occur. As a result, in the reaction solution filled in the kettle, the dispersed state is maintained, and the effective amount of catalyst becomes more sufficient by promoting the rising of the catalyst. This makes polymerization more difficult to delay, makes it easier to prepare the polymer as designed, reduces the need to remove the sticking matter to the kettle, and less burdens on manufacturing operations. An advantageous effect such as is obtained.

The method for producing a polymer by the desalting polycondensation reaction of the present invention has the above-described configuration, and a polymer having a desired molecular weight can be obtained by stably and efficiently performing the desalting polycondensation reaction. Also, by-product salts and metal salt catalysts generated after the desalting polycondensation reaction step are removed by using alkali metal salts and / or alkaline earth metal salts having a large particle size as a catalyst for the desalting polycondensation reaction. When the purification process is performed by filtration, the purification process can be easily performed in a short time.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

In the following examples and comparative examples, measurement was performed using the following apparatus.
<Measurement device>
(1) Measurement of particle diameter of potassium carbonate 50 g of potassium carbonate was sieved using a stainless steel sieve having an opening of 45 μm, and the weight of the potassium carbonate particles passed through the sieve was measured.
(2) Specific surface area measurement It measured using specific surface area meter NOVA2000 (QUANTACHROME CORPORATION). Specifically, the specific surface area was calculated | required by using the potassium carbonate vacuum-dried at 200 degreeC as a sample, and measuring nitrogen adsorption amount.
(3) About 30 ml of potassium carbonate whose weight was measured was put into a measuring cylinder having a bulk specific gravity of 50 ml, and lightly tapped on the floor 30 times. The bulk specific gravity was determined by dividing the weight of potassium carbonate by the capacity after tapping.
(4) Molecular weight measurement It measured using the high-speed GPC apparatus: HLC-8220GPC (made by Tosoh Corporation).
Measurement conditions: Developing solvent THF
Column TSK-gel GMHXL x 2 eluent flow rate 1 ml / min
Column temperature 40 ° C

Example 1
When potassium carbonate FG (Asahi Glass Co., Ltd.) was used, 150.7 g (270 mmol) of BPDE, 90.8 g (270 mmol) of BisAF, 70 × g of molecular sieve 3A 20 × 30, and 650 g of MEK were mixed. After confirming dissolution of BPDE and BisAF, 50.4 g (365 mmol) of potassium carbonate FG (manufactured by Asahi Glass) was added, and polymerization was carried out at 79 ° C. for 7.5 hours. The weight average molecular weight of the obtained polymer was 63,000. Thereafter, 700 g of MIBK was added.
After cooling, this solution was subjected to pressure filtration (filtration area φ142 mm) at a pressure of 0.03 MPa using a 300-mesh wire net. For convenience of the apparatus, it was put into the filter in two steps, and the filtration time (total of two times) was shown.
The solution after filtration was separated and washed with MIBK and water, and MIBK was concentrated to obtain a polymer.

Example 2
When potassium carbonate FG (manufactured by Asahi Glass) was used: BPDE 111.7 g (200 mmol), BPF 70.1 g (200 mmol), molecular sieve 3A 20 × 30 60 g, and MEK 800 g were mixed. After confirming dissolution of BPDE and BPF, 69.1 g (500 mmol) of potassium carbonate FG (manufactured by Asahi Glass) was added and polymerization was carried out at 79 ° C. for 7.5 hours. The weight average molecular weight of the obtained polymer was 64000. Thereafter, 550 g of MIBK was added.
The following was performed in the same manner as in Example 1 to obtain a polymer.

Example 3
When potassium carbonate FG (Asahi Glass) is used, BPDEs (4,4′-bis (2,3,4,5,6-pentafluorobenzoyloxy) diphenyl ether) 118.0 g (200 mmol), BisAF 67.3 g (200 mmol) ), Molecular sieve 3A 20 × 30 70 g, and MEK 720 g were mixed. After confirming dissolution of BPDEs and BisAF, 33.2 g (240 mmol) of potassium carbonate FG (manufactured by Asahi Glass) was added, and polymerization was carried out at 79 ° C. for 6.5 hours. The weight average molecular weight of the obtained polymer was 68,000. Thereafter, 600 g of MIBK was added.
The following was performed in the same manner as in Example 1 to obtain a polymer.

Example 4
The same conditions were carried out except that 50.4 g (365 mmol) of potassium carbonate FG (manufactured by Asahi Glass) of Example 1 was changed to 46.7 g (338 mmol) of potassium carbonate FG and 3.7 g (27 mmol) of potassium carbonate fine powder.
The polymerization time was 7 hours and 15 minutes, and the weight average molecular weight of the obtained polymer was 60000.
The following measurements were made in the same manner as in Example 1.

Comparative Example 1
The same operation was performed except that potassium carbonate FG (manufactured by Asahi Glass) of Example 1 was changed to potassium carbonate (manufactured by Asahi Glass).
The polymerization time was 5 hours, and the weight average molecular weight of the obtained polymer was 4000.
The following were tested in the same manner as in Example 1.

Comparative Example 2
The same procedure as in Example 1 was repeated except that potassium carbonate FG (Asahi Glass) was changed to potassium carbonate (Nihon Soda).
The polymerization time was 5 hours, and the weight average molecular weight of the obtained polymer was 5800.
The operation was interrupted here because the polymerization did not proceed.

Comparative Example 3
The same procedure was performed except that the potassium carbonate FG (produced by Asahi Glass Co., Ltd.) of Example 1 was changed to potassium carbonate fine powder (produced by Nippon Soda).
When the polymerization was carried out for 3 hours, the operation was interrupted here due to gelation.

Comparative Example 4
BPDE 150.7 g (270 mmol), BisAF 90.8 g (270 mmol), molecular sieve 3A 20 × 30 70 g, and MEK 650 g were mixed. After confirming dissolution of BPDE and BisAF, 41.0 g (297 mmol) of potassium carbonate fine powder (manufactured by Nippon Soda) was added, and polymerization was carried out at 79 ° C. for 5 hours. The weight average molecular weight of the obtained polymer was 75,000. Thereafter, 700 g of MIBK was added.
The following was performed in the same manner as in Example 1 to obtain a polymer.

Comparative Example 5
BPDE 111.7 g (200 mmol), BPF 70.1 g (200 mmol), molecular sieve 3A 20 × 30 60 g, and MEK 800 g were mixed. After confirming dissolution of BPDE and BPF, 69.1 g (500 mmol) of potassium carbonate (manufactured by Asahi Glass) was added, and polymerization was carried out at 79 ° C. for 5 hours. The weight average molecular weight of the obtained polymer was 5100.
The operation was interrupted here because the polymerization did not proceed.
These results are shown in Table 1 below.

From the results of Table 1, in Comparative Examples 1, 2 and 5, the molecular weight of the produced polymer is about 5000, so the filtration process was completed in a very short time. In this case, the polymer does not have a molecular weight enough to exhibit sufficient performance as a film or a molded product, and a polymer advantageous in terms of the above performance cannot be produced. In Comparative Example 3, gelation occurred during the production, and a polymer that was advantageous in terms of performance could not be produced. Further, in Comparative Example 4, a polymer having a molecular weight advantageous in terms of performance could be produced, but clogging occurred almost in the subsequent filtration step, and filtration was performed even after a sufficient time of 1 hour or more. Could not be completed. On the other hand, in Examples using potassium carbonate having a large particle diameter and a large specific surface area as a catalyst, any polymer having a desirable molecular weight can be produced, and a filtration step after the production is also possible. It was possible to carry out in a short time.

It should be noted that the influence of the shape of the alkali metal salt catalyst and / or alkaline earth metal salt catalyst particles in the method for producing a polymer by the desalting polycondensation reaction of the present invention has been clarified from the above examples and comparative examples. If conceptually expressed, for example, it is as shown in Table 2 below.

When an alkali metal salt catalyst and / or alkaline earth metal salt catalyst having a large particle size and a large specific surface area is used in the method for producing a polymer by the desalting polycondensation reaction of the present invention, the particle size is large. Therefore, when filtration is performed as a purification step of the polymer produced after the reaction, the filter paper is not covered with the film-like substance formed by the produced polymer and the basic metal salt particles, and thus filtration is not performed. It was not inhibited and the purification step after the desalting polycondensation reaction step could be easily performed in a short time. In addition, since an alkali metal salt catalyst and / or an alkaline earth metal salt catalyst having a large specific surface area is used, even in the desalting polycondensation reaction, a reaction comparable to that obtained by pulverizing the basic metal salt catalyst. Was able to be realized.

Claims (5)

A method for producing a desalted polycondensation polymer comprising a step of performing a desalting polycondensation reaction using an alkali metal salt catalyst and / or an alkaline earth metal salt catalyst,
The desalting polycondensation reaction step is an alkali metal salt catalyst and / or alkaline earth metal salt catalyst having a specific surface area of 0.8 m ² / g or more and having a mesh size of 45 μm as measured by a sieving method. A method for producing a desalted polycondensation polymer, characterized in that a powdery substance whose amount passing through a sieve is 20% by mass or less is used. The method for producing the desalted polycondensation polymer includes a step of filtering the alkali metal salt catalyst and / or the alkaline earth metal salt catalyst after the desalting polycondensation reaction step. A process for producing the desalted polycondensation polymer as described. The method for producing a desalted polycondensation polymer according to claim 1 or 2, wherein the desalting polycondensation reaction step uses an aprotic polar solvent as a solvent. The method for producing a desalted polycondensation polymer according to any one of claims 1 to 3, wherein the desalted polycondensation polymer is a fluorine-containing aromatic polymer. The fluorine-containing aromatic polymer has the following general formula (1);

(Wherein, Z is the same or different and represents a divalent organic group or a direct bond. M is the same or different and represents the number of fluorine atoms added to the aromatic ring, and is an integer of 1 to 4. R ¹ is the same or different and is a divalent organic group, Y is the same or different and represents an oxygen atom or a sulfur atom), and a polymer having a repeating unit having a structure represented by: And / or the following general formula (2):

Wherein R ¹ is the same or different and is a divalent organic group. R ² is the same or different and is an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, An alkylamino group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms, which are substituted 5. The process for producing a desalted polycondensation polymer according to claim 1, wherein the polymer has a repeating unit having a structure represented by: .