JP3609443B2 - Method for producing polyether - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a method for producing a polyether.
[0002]
[Prior art]
Conventionally, as a method for producing a polyether, as disclosed in Japanese Patent Publication No. 42-7799, an alkali metal hydroxide and a dihydric phenol monomer are reacted in a polar solvent (for example, dimethyl sulfoxide, sulfolane). There is a method in which a dialkali salt of a dihydric phenol is produced, and then a dihalo monomer is added for polymerization.
[0003]
(See the following reaction formulas (4) and (5))
[0004]
[Formula 4]
[0005]
(Wherein R⁵Is -SO₂-, -S-, -CO- or
[0006]
[Chemical formula 5]
[0007]
R⁶, R⁷Represents H, an alkyl group having 13 or less carbon atoms or an aryl group)
[0008]
[Chemical 6]
[0009]
(Wherein R⁸Is -SO₂-, -S-, -CO- or -O-, X represents Cl, Br or I)
When a high molecular weight polymer is to be obtained by this reaction, the molar ratio of the dihydric phenol monomer to the dihalobenzenoid monomer needs to be approximately 1: 1. However, when halobenzenoid monomer is present in the first stage of the reaction (upper formula (4)) during the potassium chlorination of the dihydric phenol monomer, potassium hydroxide is halogenated as shown in the following formula (6). This causes a side reaction called hydroxylation (OH) of the halogen moiety of the monomer having a group, and the balance of the molar ratio of the dihydric phenol monomer to the dihalobenzenoid monomer is lost, and only a low molecular weight polymer is obtained.
[0010]
[Chemical 7]
[0011]
(Wherein R⁹Is -SO₂Represents-, -S-, -CO- or -O-)
Therefore, the first problem is that the dihalobenzenoid monomer must be added after the potassium chlorination of the dihydric phenol monomer is completed, and the amount of potassium hydroxide added is strictly twice that of the dihydric phenol monomer. It had the disadvantage that it was necessary to make a quantity. Furthermore, in order to produce the above-mentioned side reaction, it had the fault that a hydroxyhalobenzenoid monomer could not be copolymerized with each said monomer.
[0012]
The second problem is that the polymer used in the polymerization reaction and the solvent for dissolving the alkali metal salt are liquid at room temperature or their freezing point is close to room temperature, and even if the solution is cooled at the end of the weight reaction, the liquid or It is a slurry. Therefore, when the polymer is purified and recovered from the solution after completion of the polymerization reaction, in order to remove the alkali metal salt that is a by-product, the polymer is a poor solvent for the polymer after the solution is once diluted with a polymer good solvent. A refining method called a reprecipitation method in which a polymer is precipitated in a liquid must be taken. At that time, a huge amount of reprecipitation solvent is required, and the yield of the polymer obtained by one washing is low.
[0013]
[Problems to be solved by the invention]
To solve these problems, as shown in the following formulas (7) and (8), divalent phenol, alkali metal carbonate and dihalobenzenoid are simultaneously mixed in diphenylsulfone (Japanese Patent Laid-Open No. 53-112998). Alternatively, a method of polymerizing by heating in an amide polar solvent represented by N-methyl-2-pyrrolidone (Japanese Patent Publication No. 61-5488) has been proposed.
[0014]
[Chemical 8]
[0015]
(Wherein R¹⁰Is
[0016]
[Chemical 9]
[0017]
Represents R¹², R¹³Represents H, an alkyl group having 8 or less carbon atoms or an aryl group)
[0018]
[Chemical Formula 10]
[0019]
(Wherein R¹¹Is -SO₂Represents-, -S-, -CO- or -O-)
In this method, an alkali metal carbonate which is a weaker base than an alkali metal hydroxide is used as a reaction aid. Therefore, even if the molar amount of the alkali metal in the alkali metal carbonate is slightly more than the molar amount of the hydroxyl group in the phenol monomer, the problem of attacking the halogen portion of the monomer does not occur, and the hydroxyhalobenzenoid It can also be copolymerized with monomers.
[0020]
However, when a liquid having a high proton accepting ability such as an amide solvent represented by N-methyl-2-pyrrolidone or the like is used as a polymerization solvent, these solvents are liquid at room temperature. In order to remove the inorganic salt that is a by-product when producing and recovering the product, as in the above Japanese Patent Publication No. 42-7799, it is necessary to take an inefficient washing method called a reprecipitation method, It is not a solution for the second problem.
[0021]
By the way, when a monomer is polymerized using a solvent that is solid at room temperature typified by diphenylsulfone, the reaction product is solidified when the solution is cooled at the end of the polymerization. In this method, the purification of the polymer can be performed by a more efficient method called a pulverization method in which impurities are extracted by sequentially using a solvent that dissolves diphenylsulfone and a solvent that dissolves an inorganic salt as a by-product. Seems to give a solution to both the first and second problems.
[0022]
However, the general formula (9)
[0023]
Embedded image
[0024]
(Wherein R¹⁴, R¹⁵Represents H, an alkyl group or an aryl group)
As shown in FIG. 2, an electron-withdrawing group (—S—, —CO—, —SO₂In the case of using a dihydric phenol monomer having no-etc.), the acidity of the monomer (the ability to dissociate the proton group of the dihydric phenol) is low, so in a solvent having a low proton accepting ability such as diphenyl sulfone, (7) Alkali metal chlorination of the monomer represented by the formula does not proceed and the polymerization cannot be performed.
[0025]
The present invention has been made in order to eliminate the above-mentioned drawbacks. The object of the present invention is to provide a monomer having low acidity (S, SO₂, CO, O, etc., which do not have a structure), the product can be recovered in the form of a solidified product, and thus the polymer can be purified and recovered by the pulverization extraction method. It is to provide a method for producing ether.
[0026]
[Means for Solving the Problems]
In view of the above problems, the present inventor has intensively studied, and as a result, found the present manufacturing method and completed the present invention.
[0027]
That is, the present invention relates to the general formula (1)
[0028]
Embedded image
[0029]
Wherein a and b are integers from 0 to 4, R¹And R²Are each independently H, an alkyl or aryl group having 8 or less carbon atoms, A¹And A²Each independently represents an alkyl or aryl group having 1 to 8 carbon atoms)
A divalent phenol monomer represented by:
General formula (2)
[0030]
Embedded image
[0031]
Wherein c and d are integers from 0 to 4, A³And A⁴Are each independently an alkyl or aryl group having 1 to 8 carbon atoms, R³Is -SO₂-, -S-, -CO-, or -O-, X represents F, Cl, Br or I)
A dihalobenzenoid monomer represented by
General formula (1), (2) and general formula (3)
[0032]
Embedded image
[0033]
(Wherein R^FourIs -SO₂-, -S-, -CO- or -O-, X represents F, Cl, Br or I, and n represents 1 or 2)
In a method for synthesizing and recovering a polyether from a hydroxyhalobenzenoid monomer represented by:
(1)A mixed solvent comprising diphenylsulfone, an amide solvent having a boiling point of 150 ° C. or higher and 240 ° C. or lower, and an azeotropic solvent with water having a boiling point of 100 ° C. or higher and 200 ° C. or lower, wherein the content ratio of the amide solvent is In the presence of a mixed solvent that is 100 parts by weight or more with respect to 100 parts by weight of diphenylsulfone,The total amount of the monomers represented by the general formulas (1), (2), and (3) is 5 to 500 parts by weight with respect to 100 parts by weight of diphenylsulfone,Heating the monomer mixture and the alkali metal carbonate in a temperature range of 100 to 200 ° C. in the presence of an alkali metal carbonate at an equivalent ratio of 1 to 1.2 relative to the equivalent of the hydroxyl group in the monomer mixture. The divalent phenol monomer and the alkali metal carbonate are reacted while continuously removing water present in the system by refluxing and dehydrating the azeotropic solvent, and then at a temperature of 240 to 320 ° C. Polymerization is performed while removing the amide solvent and the azeotropic solvent to 15% or less of the total solvent weight by heating in a range.Or
(2) A mixed solvent containing diphenyl sulfone, an amide solvent having a boiling point of 150 ° C. or higher and 240 ° C. or lower, and an azeotropic solvent with water having a boiling point of 100 ° C. or higher and 200 ° C. or lower, the content ratio of the amide solvent In the presence of a mixed solvent that is 100 parts by weight or more with respect to 100 parts by weight of the diphenylsulfone,
Heating the monomer mixture and the alkali metal carbonate in a temperature range of 100 to 200 ° C. in the presence of an alkali metal carbonate at an equivalent ratio of 1 to 1.2 relative to the equivalent of the hydroxyl group in the monomer mixture. The dihydric phenol monomer and the alkali metal carbonate are reacted while continuously removing water present in the system by refluxing and dehydrating the azeotropic solvent,
Next, the polymer is polymerized while removing the amide solvent and the azeotropic solvent to 15% or less of the total solvent weight by heating in a temperature range of 240 to 320 ° C.
Furthermore, the alkali metal salt produced as a by-product should be removed by the pulverization extraction method.
Is a method for producing a polyether.
[0034]
The dihydric phenol monomer represented by the general formula (1) used in the present invention has a central portion.
[0035]
Embedded image
[0036]
As shown by electron-withdrawing groups (—S—, —CO—, —SO₂-, -O-, etc.) and R¹, R²Specifically, H or the following alkyl group or aryl group can be mentioned.
[0037]
As an alkyl group:
[0038]
Embedded image
[0039]
As an aryl group:
[0040]
Embedded image
[0041]
In formula (1), A¹, A²Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, and butyl groups; and the aryl group includes phenyl, 4-methylphenyl, 3-netylphenyl, and 3,5-dimethylphenyl groups.
[0042]
Specific examples include the following.
[0043]
4,4′-methylenebisphenol (bisphenol F), 4,4′-ethylidene-bisphenol, 2,2′-methylenebis (4-methylphenol), 4,4′-methylenebis (2,6-dimethylphenol), 2 , 2′-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2′-bis (3-methyl-4-hydroxyphenyl) propane (bisphenol C), 4,4 ′-(1,3-dimethyl) Butylidene) bisphenol, 2,2′-bis (3,5-dimethyl-4-hydroxyphenyl) propane (tetramethylbisphenol A), 4,4 ′-(1-phenylethylidene) bisphenol (bisphenol AP), 2 ′ -Bis (3-methyl-4-hydroxyphenyl) propane, 5,5 '-(1-methylethylidene (1,1'-biphenyl) 2-ol.
[0044]
More preferably, bisphenol A, bisphenol F, or bisphenol AP is used.
[0045]
R of the dihalobenzenoid represented by the general formula (2) used in the present invention³-S-, -SO₂An electron-withdrawing group selected from the group consisting of-, -CO- and -O-;³, A⁴Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, and butyl groups, and the aryl group includes phenyl, 4-methylphenyl, 3-methylphenyl, and 3,5-dimethylphenyl groups.
[0046]
Specific examples include the following.
[0047]
4,4′-difluorodiphenylsulfone, 4,4′-dichlorodiphenylsulfone, 4,4′-dibromodiphenylsulfone, 4,4′-diiododiphenylsulfone, bis (2-methyl-4-chlorophenyl) sulfone, bis (2-methyl-4-chlorophenyl) sulfone, bis (2,5-dimethyl-4-chlorophenyl) sulfone, bis (2-methyl-4-fluorophenyl) sulfone, bis (2,5-dimethyl-4-fluorophenyl) ) Sulfone, bis (2-methyl-4-bromophenyl) sulfone, bis (2,5-dimethyl-4-bromophenyl) sulfone, bis (2-methyl-4-iodophenyl) sulfone, bis (2,5- Dimethyl-4-iodophenyl) sulfone, bis (2-phenyl-4-fluorophenyl) sulfone, Scan (2-phenyl-4-chlorophenyl) sulfone, bis (2-phenyl-4-bromophenyl) sulfone, bis (2-phenyl-4-iodophenyl) sulfone;
4,4′-difluorodiphenyl ketone, 4,4′-dichlorodiphenyl ketone, 4,4′-dibromodiphenyl ketone, 4,4′-diiododiphenyl ketone, bis (2-methyl-4-chlorophenyl) ketone, bis (2-methyl-4-chlorophenyl) ketone, bis (2,5-dimethyl-4-chlorophenyl) ketone, bis (2-methyl-4-fluorophenyl) ketone, bis (2,5-dimethyl-4-fluorophenyl) ) Ketone, bis (2-methyl-4-bromophenyl) ketone, bis (2,5-dimethyl-4-bromophenyl) ketone, bis (2-methyl-4-iodophenyl) ketone, bis (2,5- Dimethyl-4-iodophenyl) ketone, bis (2-phenyl-4-fluorophenyl) ketone, bis (2-phenyl-4-chloro) Phenyl) ketone, bis (2-phenyl-4-bromophenyl) ketone, bis (2-phenyl-4-iodophenyl) ketone;
4,4′-difluorodiphenyl sulfide, 4,4′-dichlorodiphenyl sulfide, 4,4′-dibromodiphenyl sulfide, 4,4′-diiododiphenyl sulfide, bis (2-methyl-4-chlorophenyl) sulfide, bis (2-methyl-4-chlorophenyl) sulfide, bis (2,5-dimethyl-4-chlorophenyl) sulfide, bis (2-methyl-4-fluorophenyl) sulfide, bis (2,5-dimethyl-4-fluorophenyl) ) Sulfide, bis (2-methyl-4-bromophenyl) sulfide, bis (2,5-dimethyl-4-bromophenyl) sulfide, bis (2-methyl-4-iodophenyl) sulfide, bis (2,5- Dimethyl-4-iodophenyl) sulfide, bis (2-phenyl-4-phenyl) Orofeniru) sulfide, bis (2-phenyl-4-chlorophenyl) sulfide, bis (2-phenyl-4-bromophenyl) sulfide, bis (2-phenyl-4-iodophenyl) sulfide;
4,4′-difluorodiphenyl ether, 4,4′-dichlorodiphenyl ether, 4,4′-dibromodiphenyl ether, 4,4′-diiododiphenyl ether, bis (2-methyl-4-chlorophenyl) ether, bis (2-methyl -4-chlorophenyl) ether, bis (2,5-dimethyl-4-chlorophenyl) ether, bis (2-methyl-4-fluorophenyl) ether, bis (2,5-dimethyl-4-fluorophenyl) ether, bis (2-methyl-4-bromophenyl) ether, bis (2,5-dimethyl-4-bromophenyl) ether, bis (2-methyl-4-iodophenyl) ether, bis (2,5-dimethyl-4-) Iodophenyl) ether, bis (2-phenyl-4-fluorophenyl) ether, Scan (2-phenyl-4-chlorophenyl) ether, bis (2-phenyl-4-bromophenyl) ether, bis (2-phenyl-4-iodophenyl) ether.
[0048]
In particular, the following are preferred from the viewpoint of ease of polymerization and availability. 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl ketone, 4,4'-dichlorodiphenyl ketone.
[0049]
The hydroxyhalobenzenoid compound represented by the general formula (3) used in the present invention is R⁴-S-, -SO₂An electron-withdrawing group selected from the group consisting of —, —CO— and —O—, and specifically includes the following.
[0050]
4-chloro-4'-hydroxydiphenylsulfone, 4-chloro-4 '-(P-hydroxyphenyl) diphenylsulfone4-Chloro-4'-hydroxydiphenyl ketone, 4-chloro-4 '-(P-hydroxyphenyl) diphenyl ketone4-Chloro-4'-hydroxydiphenyl sulfide, 4-chloro-4 '-(P-hydroxyphenyl) diphenylsulfiDe;
4-fluoro-4'-hydroxydiphenylsulfone, 4-fluoro-4 '-(P-hydroxyphenyl) diphenylsulfone4-Fluoro-4'-hydroxydiphenyl ketone, 4-fluoro-4 '-(P-hydroxyphenyl) diphenyl ketone4-Fluoro-4'-hydroxydiphenyl sulfide, 4-fluoro-4 '-(P-hydroxyphenyl) diphenyl sulfide
In particular, 4-chloro-4 '-(P-hydroxyphenyl) diphenylsulfo is preferred because of its ease of polymerization.Inis there.
[0051]
The total amount of the monomers represented by the formulas (1), (2) and (3) is preferably 5 to 500 parts by weight with respect to 100 parts by weight of diphenylsulfone which is one of the solvents. If the amount is less than 5 parts by weight, the yield of the polymer obtained by one polymerization is lowered, and if it exceeds 500 parts by weight, it is difficult to crush during the pulverization process, and the purification rate is remarkably lowered.
[0052]
In the production method of the present invention, an azeotropic solvent of diphenyl sulfone, an amide solvent, and water is used as a solvent for reacting and polycondensing the phenol monomer (1), the dihalobenzenoid monomer (2) and the alkali metal salt. Although it is characterized by using three kinds of mixed solvents, the following is also a major feature.
[0053]
First, by stirring at 100 to 200 ° C., water that promotes dissociation of hydrogen ions of the phenol monomer by the proton accepting power of the amide solvent, and further generates water that inhibits the reaction during alkali metalation, By refluxing and dehydrating with an azeotropic solvent, even a low acidity monomer having no active structure in the center can be easily alkali metalized.
[0054]
Next, the polymerization is carried out at 240 to 320 ° C., and the amide solvent which has finished its function is removed from the system, and finally it is obtained in the state of a mixture of diphenylsulfone and polymer.
[0055]
The solvent azeotroped with water used in the present invention is used to remove water that inhibits the reaction during potassium chlorination, and has a boiling point of 100 ° C. or higher and 200 ° C. or lower. If an azeotropic solvent having a boiling point exceeding 200 ° C. is used, the amide solvent is also not preferable because it evaporates from the polymerization kettle, and if the boiling point is less than 100 ° C., it is not preferable because it does not efficiently azeotrope with water. Absent. In addition, in order to return only the azeotropic solvent to the polymerization kettle after liquefaction in the cooling device, it causes two-phase separation rapidly with water, that is, is immiscible with water and has a specific gravity different from that of water. It is preferable that Preferably, toluene, chlorobenzene or the like is used.
[0056]
The amide solvent used in the present invention has a boiling point of 150 ° C. or higher in order to prevent being distilled out together with the azeotropic solvent during alkali metal chlorination, and is polymerized to drive out of the system during the subsequent polymerization. It has a boiling point below the temperature (for example, 240 ° C.).
[0057]
N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylimidazoline and the like are preferably used. The weight ratio of the amide solvent to diphenyl sulfone is 100 parts by weight or more of the amide solvent with respect to 100 parts by weight of diphenyl sulfone, and preferably 100 to 500 parts by weight of the amide solvent with respect to 100 parts by weight of diphenyl sulfone. It is. If the amount of the amide solvent is less than 100 parts by weight with respect to the weight of diphenylsulfone, the degree of polymerization will extremely decrease, and if it exceeds 500 parts by weight, the capacity of the weight kettle required to produce the same amount will increase, and the cost will increase. Is unfavorable because it increases.
[0058]
As the alkali metal carbonate used in the present invention, sodium carbonate, potassium carbonate, rubidium carbonate, potassium oxalate, potassium bicarbonate and the like are preferable, and potassium carbonate or sodium carbonate is particularly preferable. The amount of the alkali metal carbonate is such that the equivalent ratio is between 1 and 1.2 with respect to the equivalents of hydroxyl groups in all monomers present in the system. If the equivalent ratio is less than 1, the polymerization reaction does not proceed, and if it exceeds 1.2, the side reaction becomes violent.
[0059]
Moreover, the temperature of the first alkali metal chloride is 100-200 degreeC. If it is less than 100 ° C., removal of water by azeotropy hardly proceeds, and if it exceeds 200 ° C., the amide solvent required in the system is evaporated, which is not preferable. Moreover, the temperature of the next polymerization process is 240-320 degreeC. If the temperature is lower than 240 ° C., the evaporation rate of the amide solvent, which is a liquid component, decreases, so that it cannot be recovered in the form of a solidified product at the end of the polymerization, and if it exceeds 320 ° C., coloring due to side reactions, gelation, main chain This is not preferable.
[0060]
In the method for producing the polyether of the present invention, an alkali metal salt is produced as a by-product, but the alkali is added together with the polymerization solvent used by a known method such as a pulverization extraction method in which the solidified product is pulverized and then filtered or leached. Metal salts can be removed.
[0061]
【Example】
Hereinafter, although the Example regarding this invention is described, it does not restrict | limit this invention with this.
[0062]
(Example 1)
25.68 parts by weight of 2,2-bis- (4-hydroxyphenyl) propane (hereinafter referred to as BisA) as a monomer was added to a reaction vessel equipped with a condenser equipped with a stirrer, a gas introduction tube, a thermometer, and a Dane Stark tube. 4,4′-dichlorodiphenylsulfone (hereinafter referred to as DCDPS) 32.33 parts by weight, 4-chloro-4 ′-(P-hydroxyphenyl) diphenylsulfone (hereinafter referred to as PBPS) 25.9 parts by weight, and further anhydrous Nitrogen substitution was performed by charging 22.8 parts by weight of potassium carbonate and 100 parts by weight of diphenylsulfone (hereinafter referred to as DPS).
[0063]
Next, 100 parts by weight of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 100 parts by weight of toluene were charged in a nitrogen atmosphere, and the temperature was increased while stirring. When the temperature reached 170 ° C., the temperature increase was stopped, and in that state, toluene and water were azeotroped for 5 hours to perform reflux dehydration. Next, the temperature was raised to 260 ° C., and the polymerization reaction was carried out for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain a brown solid.
[0064]
When the obtained solid was dissolved in orthochlorophenol and the remaining amount of NMP was measured by liquid chromatography, it was confirmed that it was contained at a rate of 1% in the total solvent. In addition, it was confirmed that toluene did not remain at all.
[0065]
The solidified sample was coarsely pulverized to a particle size of 1 mm with a pulverizer, poured with 1.8 liters of acetone, and finely pulverized with a homogenizer. Further, the mixed solvent was completely extracted by washing the sample twice with 1.8 liters of acetone, and potassium chloride was completely removed by washing with 1.8 liters of water three times. Drying at 24 ° C. for 24 hours gave a white powder polymer.
[0066]
The obtained polymer was measured for reduced viscosity at a concentration of 1 g / dl in dimethylformamide at 30 ° C. Next, this polymer was press-molded into a flat plate of 50 × 50 × 105 mm at a temperature of 300 ° C. to obtain a colorless and transparent plate. The total light transmittance of this plate was measured and found to be 89%. The above results are shown in Table 1. (Example 2)
As monomers, 34.24 parts by weight of BisA and 43.07 parts by weight of DCDPS were charged, and the polymerization reaction was carried out in the same manner as in Example 1. After completion of the reaction, the reaction solution was cooled to room temperature to obtain a brown solidified sample. Further, pulverization and purification were performed in the same manner as in Example 1, and a white powder polymer was obtained.
[0067]
The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0068]
(Example 3)
The operations for monomer, catalyst, solvent amount and subsequent reflux dehydration were carried out in the same manner as in Example 1.
[0069]
Next, in the process of raising the temperature to 260 ° C. and performing the polymerization reaction as it is for 5 hours, NMP is 94.8 parts by weight so that 5% (mass% of NMP in the residual solvent) of NMP remains in the system. When it was distilled off, the drain cock of the Dane-Stark tube was closed to recirculate NMP. After completion of the reaction, the reaction solution was cooled to room temperature to obtain a brown solid.
[0070]
When the obtained solid was dissolved in orthochlorophenol and the remaining amount of NMP was measured by liquid chromatography, it was confirmed that it was contained in a proportion of 5% in the total solvent.
[0071]
The solidified sample was processed and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0072]
(Example 4)
In Example 3, when 82.4 parts by weight of NMP was distilled off, the drain cock was closed so that NMP was refluxed. After completion of the reaction, the reaction solution was cooled to room temperature to obtain a brown solid.
[0073]
When the obtained solid was dissolved in orthochlorophenol and the remaining amount of NMP was measured by liquid chromatography, it was confirmed that it was contained at a ratio of 15% in the total solvent. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
[0074]
(Comparative Example 1)
Polymerization was carried out in the same manner as in Example 1 except that 100 parts by weight of DPS, 100 parts by weight of NMP, and toluene were changed to 0.
[0075]
After completion of the reaction, the mixture was cooled to obtain a brown solid. Thereafter, washing was performed in the same manner as in Example 1 to obtain a brown powder. Thereafter, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0076]
(Comparative Example 2)
Polymerization was carried out in the same manner as in Example 1 except that 100 parts by weight of DPS, 100 parts by weight of toluene, and 0 of NMP were used as solvents.
[0077]
A reddish brown solid was obtained after the reaction. Thereafter, washing was carried out in the same manner as in Example 1, but no solid matter was obtained.
[0081]
(Comparative example3)
Polymerization was performed in the same manner as in Example 1 except that the blending ratio of DPS and NMP was changed to 3: 1 by weight to obtain a brown solid. Thereafter, purification and evaluation were performed in the same manner as in Example 1, and the results are shown in Table 1.
[0082]
(Comparative example4)
Potassium carbonate vs monomerThisPolymerization was carried out in the same manner as in Example 1 except that the quantitative ratio was changed to 0.9. The results are shown in Table 1.
[0083]
(Comparative example5)
Potassium carbonate vs monomerThisPolymerization was carried out in the same manner as in Example 1 except that the quantitative ratio was changed to 2.0. The results are shown in Table 1.
[0084]
(Comparative example6)
Polymerization was carried out in the same manner as in Example 1 except that the reflux dehydration temperature was changed to 90 ° C. The results are shown in Table 1.
[0085]
(Comparative example7)
Polymerization was carried out in the same manner as in Example 1 except that the reflux dehydration temperature was changed to 250 ° C. The results are shown in Table 1.
[0086]
(Comparative example8)
Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 180 ° C. The obtained sample was liquid and 45% of NMP remained. Pour 1 liter of N, N-dimethylformamide into this sample,Next, the solution was poured into a mixed solvent of a total of 18 liters of 9 liters of methanol and 9 liters of acetone, and precipitated while stirring with a homogenizer. Then, the reaction by-product is completely removed by washing successively with 1.8 liters of methanol twice and 1.8 liters of water three times, followed by vacuum drying at 120 ° C. for 24 hours to obtain a white polymer powder. Got.Evaluation was performed. The results are shown in Table 1.
[0087]
(Comparative example9)
Polymerization was carried out in the same manner as in Example 1 except that only 200 parts by weight of NMP and 100 parts by weight of toluene were used as the solvent, the reflux dehydration temperature was 160 ° C., and the polymerization temperature was 180 ° C.
[0088]
The obtained sample was liquid. After the comparative example8In the same manner as above, a polymer was obtained and evaluated. The results are shown in Table 1.
[0089]
[Table 1]
[0090]
【The invention's effect】
The production method according to the present invention has a low acidity monomer (S, SO₂Even when a polyether is produced using a compound having no structure such as CO, O, etc., the product can be recovered in the form of a solidified product. From this, in order to remove the alkali metal salt as a by-product, the polymer can be purified and recovered by a pulverization extraction method instead of the reprecipitation method.
[0091]
Therefore, a reprecipitation tank (used to precipitate the polymer in a liquid that is a poor solvent for the polymer) having a volume more than 10 times the washing tank used in the pulverization extraction method, and the accompanying reprecipitation solvent The recovery and purification process can be omitted.
[0092]
Therefore, in the purification process, the amount of the solvent to be used can be reduced, and the industrial value is great in terms of space saving and cost reduction.

Claims (2)

General formula (1)
(Wherein, a and b are integers of 0 to 4, R ¹ and R ² are each independently H, an alkyl group or aryl group having 8 or less carbon atoms, and A ¹ and A ² are each independently 1 carbon atom. Represents an alkyl group or an aryl group of ~ 8)
A divalent phenol monomer represented by
General formula (2)
(Wherein c and d are integers of 0 to 4, A ³ and A ⁴ are each independently an alkyl group or aryl group having 1 to 8 carbon atoms, R ³ is —SO ₂ —, —S—, —CO; -, Or -O-, X represents F, Cl, Br or I)
Or a dihalobenzenoid monomer represented by the general formulas (1), (2) and (3)
(Wherein R ⁴ represents —SO ₂ —, —S—, —CO— or —O—, X represents F, Cl, Br or I, and n represents 1 or 2)
In a method for synthesizing and recovering a polyether from a hydroxyhalobenzenoid monomer represented by:
A mixed solvent comprising diphenylsulfone, an amide solvent having a boiling point of 150 ° C. or higher and 240 ° C. or lower, and an azeotropic solvent with water having a boiling point of 100 ° C. or higher and 200 ° C. or lower, wherein the content ratio of the amide solvent is In the presence of a mixed solvent that is 100 parts by weight or more with respect to 100 parts by weight of diphenylsulfone,
The total amount of the monomers represented by the general formulas (1), (2), and (3) is 5 to 500 parts by weight with respect to 100 parts by weight of diphenylsulfone,
Heating the monomer mixture and the alkali metal carbonate in a temperature range of 100 to 200 ° C. in the presence of an alkali metal carbonate at an equivalent ratio of 1 to 1.2 relative to the equivalent of the hydroxyl group in the monomer mixture. Then, while continuously removing water existing in the system by refluxing and dehydrating the azeotropic solvent, the dihydric phenol monomer and the alkali metal carbonate are reacted,
Next, the polymer is polymerized while being heated in a temperature range of 240 to 320 ° C. while removing the amide solvent and the azeotropic solvent to 15% or less of the total solvent weight. A method for producing a polyether. General formula (1)
Wherein a and b are integers from 0 to 4, R ¹ And R ² Are each independently H, an alkyl or aryl group having 8 or less carbon atoms, A ¹ And A ² Each independently represents an alkyl or aryl group having 1 to 8 carbon atoms)
A divalent phenol monomer represented by:
General formula (2)
Wherein c and d are integers from 0 to 4, A ^Three And A ^Four Are each independently an alkyl or aryl group having 1 to 8 carbon atoms, R ^Three Is -SO ₂ -, -S-, -CO-, or -O-, X represents F, Cl, Br or I)
A dihalobenzenoid monomer represented by
General formula (1), (2) and general formula (3)
(Wherein R ^Four Is -SO ₂ -, -S-, -CO- or -O-, X represents F, Cl, Br or I, and n represents 1 or 2)
In a method for synthesizing and recovering a polyether from a hydroxyhalobenzenoid monomer represented by:
A mixed solvent comprising diphenylsulfone, an amide solvent having a boiling point of 150 ° C. or higher and 240 ° C. or lower, and an azeotropic solvent with water having a boiling point of 100 ° C. or higher and 200 ° C. or lower, wherein the content ratio of the amide solvent is In the presence of a mixed solvent that is 100 parts by weight or more with respect to 100 parts by weight of diphenylsulfone,
Heating the monomer mixture and the alkali metal carbonate in a temperature range of 100 to 200 ° C. in the presence of an alkali metal carbonate at an equivalent ratio of 1 to 1.2 relative to the equivalent of the hydroxyl group in the monomer mixture. Then, while continuously removing water existing in the system by refluxing and dehydrating the azeotropic solvent, the dihydric phenol monomer and the alkali metal carbonate are reacted,
Next, by heating in the temperature range of 240 to 320 ° C., the polymer is polymerized while removing the amide solvent and the azeotropic solvent to 15% or less of the total solvent weight,
Furthermore, the manufacturing method of polyether characterized by removing the alkali metal salt produced | generated as a by-product by the grinding | pulverization extraction method.