JPS6228169B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a method for producing polyarylethersulfone copolymers. Explanation of the process leading to the invention We used the formula It has been found that a polyarylether sulfone polymer having only repeating units of is dissolved in concentrated sulfuric acid (98% w/w) and sulfonated very rapidly to yield a completely water-soluble product. This is probably a subunit of the polymer. substitution of -SO ₂ OH groups on all or most of the aromatic rings of (see Examples 7 to 9), monosulfonation that occurs in the case of polymers with ether bonds placed in the ortho or para position in the subunits mentioned above. This may also be due to the disulfonation that occurs in polymers with ether bonds located in the meta position in the subunits. In contrast, we use the formula It has been found that polyarylether sulfones having only repeating units of 2 undergo virtually no sulfonation in concentrated sulfuric acid (98% w/w). Concentrated sulfuric acid dissolves the polymer but does not change it (see Example 10). Note that other sulfonating agents, such as oleum and chlorosulfonic acid, and even mixtures of concentrated sulfuric acid and small amounts of oleum, will completely sulfonate and/or decompose the polymer. (Examples 11 and 12)
reference). Therefore, the polyarylethersulfone copolymer containing the units (A) and (B) is prepared using concentrated sulfuric acid (98%
hydrophilic sulfonated copolymers (ranging up to completely water-soluble polymers) by varying the proportion of repeating units (B) in the copolymer. Gives union. Structure of the invention According to the invention, repeating units of formula (A), 1 to 99 mol%, preferably 5 to 80 mol% and correspondingly repeating units of formula (B), Provided is a method for making a polyarylethersulfone copolymer comprising 99 to 1 mole %, preferably 95 to 20 mole %. The polyarylethersulfone copolymer combines dihydroxyphenol selected from hydroquinone, catechol or resorcinol with 4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone, dihydroxyphenol and 4,4' It can be produced by condensing -dihydroxydiphenyl sulfone with 1 to 99 mol% of dihydroxyphenol based on the total amount. DETAILED DESCRIPTION OF THE INVENTION The repeating unit (A) preferably has an ether bond located at the para position, and is preferably represented by the following formula. After sulfonation, the polyarylethersulfone copolymer of the present invention contains substantially all the subunits of the copolymerized unit (A). is sulfonated, and after sulfonation said unit
Controlled sulfonation as described above can be performed to produce a hydrophilic sulfonated copolymer such that substantially all of (B) remains in the unsulfonated state. Control of the sulfonation reaction must be such that the resulting copolymer has a degree of hydrophilicity corresponding to a water absorption of about 2% by weight water at room temperature up to complete solubility in water. A sulfonated hydrophilic copolymer derived from the copolymer of the present invention (at room temperature, preferably 2 to 40
% water, more preferably from 5 to 30% water), even when they are not only characterized by hydrophilicity but also contain significant amounts of water (e.g. up to 20% water). Because it retains considerable strength (see Example 5), it is potentially useful as a membrane material, e.g. for ultrafiltration processes such as desalination and _microbial removal. The ionomers of these sulfonated copolymers are, for example, -
SO ₂ OH group is replaced by SO ₃ ^- M ⁺ (M is an alkali metal or
It can be easily prepared by converting it into a salt such as NR ₄ (R is an alkyl group). These also have use as hydrophilic polymers. Therefore, the sulfonyl group of the sulfonated copolymer derived from the copolymer of the present invention has the formula -SO ₂ OY
[In the formula, Y represents H, an alkali metal, or NR ₄ (R is an alkyl group)] is preferred. A copolymer having repeating units (A) and (B) described above can be prepared using a suitable dihydroxyphenol (e.g. Hydroquinone, catechol or resorcinol), 4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone and an alkali metal carbonate or bicarbonate. EXAMPLES The present invention will be illustrated by the following examples. Example 1 Copolymers containing repeating unit (A) (the ether bond in the subunit is in the para position) and (B) in various compositions (unit (A)
25 mol% ~ 66.7 mol%, therefore unit (B) 75 mol% ~
Using diphenyl sulfone as _a polymerization solvent, appropriate proportions of hydroquinone and 4,4'-dihydroxydiphenyl sulfone were combined with 4,4'-dichlorophenyl sulfone in the presence of _K2CO3 . It was prepared by reacting. The polymerization temperature is
The temperature was within the range of 200-290°C. Substantially equimolar components of total bisphenol and dihalide were used with a molar equivalent of K ₂ CO ₃ in excess of slightly more than two times the molar equivalent of the dihalide. The copolymer was sulfonated as follows (a 25 mol% (A)/75 mol% (B) copolymer was used as a representative example). Copolymer (20g) in concentrated sulfuric acid (98% W/W) (110g)
ml) for 18 hours to obtain a very viscous solution. Further concentrated sulfuric acid (50ml) was added and shaking continued for a further 18 hours (ie 36 hours total). This solution was then poured into distilled water (800 ml) in a Waring blender resulting in a white precipitate. The white precipitate was filtered and washed three times with fresh water in a blender with overseparation after each wash. The product was dried in a vacuum oven at about 65° C. overnight. All sulfonated copolymers were analyzed by 220MHz NMR spectroscopy to reveal that virtually all subrepeat units of the polymer chain were was shown to be monosulfonated, but none of the repeating units (B) were sulfonated.
All sulfonated products were soluble in dimethylformamide and dimethyl sulfoxide. Example 2 A copolymer containing repeating units (A) (ether bond para position of the subunit) and (B) in an amount of 80 mol% of units (A) and 20 mol% of units (B) was prepared as described in Example 1. . The sample (5 g) was shaken with concentrated sulfuric acid (98% W/W) (20 ml) overnight. Further concentrated sulfuric acid (20ml) was added and shaking continued for a further 24 hours. This solution was then poured into distilled water in a Waring blender to create a white precipitate. The white precipitate was filtered off, washed four times with water, and dried in a vacuum oven overnight. Repetition unit
(A) (ether bond para position of subunit) and (B) are respectively (A) 5 mol%/(B) 95 mol%, (A) 10 mol%/(B)
The amount of starting copolymer and the use of concentrated sulfuric acid Although the amounts were different, sulfonation was performed in the same manner as for the above copolymer (A) 80 mol %/(B) 20 mol %. Analysis of the sulfonation product by 220MHz spectroscopy revealed that the subrepeat unit of the resulting polymer chain, Virtually all of them are monosulfonated, but
It was shown that no sulfonation had occurred in any of the repeating units (B). Example 3 (Example of Use) The sodium salt of the sulfonated copolymer of Example 2 was prepared by neutralizing it in excess NaOH solution. Neutralization of a sulfonated (A) 10 mol %/(B) 90 mol % copolymer will be explained as a representative example. The sulfonated 10 mol % (A)/90 mol % (B) copolymer (50 g) of Example 2 was stirred in a solution of NaOH (30 g) in water (600 ml) overnight. Then add this mixture to 60-80
℃ overnight and cooled to 40 ℃. The product was filtered, washed four times with water and dried in the oven. The sodium content of the sulfonated (A) 10 mol%/(B) 90 mol%, (A) 20 mol%/(B) 80 mol% and (A) 40 mol%/(B) 60 mol% copolymer. Measured using flame emission spectroscopy (FES) and confirmed NMR spectroscopy showing that all units (A) are monosulfonated. The results were as follows.

[Table] Example 4 (Example of use) The water absorption before and after sulfonation of the copolymer of Example 2 and the water absorption of the neutralized sulfonated copolymer of Example 3 were measured using a dry film of the copolymer (flowed from a dimethylformamide solution). The samples were first immersed in water at room temperature for 24 hours, and then measured. The results were as follows.

[Table] Example 5 (Usage example) Sulfone of Example 2 (A) 40 mol%/(B) 60 mol% and (A)
The mechanical properties of the 80 mol%/(B) 20 mol% copolymer are
Tests were conducted in the form of a cast film both in a dry state and after water absorption. For comparison, a homopolymer containing only units (B) (not sulfonated) was also tested. The results were as follows.

[Table] Example 6 Repeating unit (A) (ether bond meta position in subunit)
A copolymer (5 g) containing 40 mol % of (A) and 60 mol % of (B) was prepared essentially according to the procedure described in Example 1 (resorcinol was used in place of hydroquinone). ). Add 5 g of this copolymer to concentrated sulfuric acid (98%
W/W) and left for 36 hours. This solution was poured into distilled water to produce a white precipitate. The white precipitate was filtered off, washed three times with water, and oven dried. The product was analyzed by 220MHz spectroscopy;
sub-repeating unit in the resulting polymer chain, It was confirmed that substantially all of the repeating unit (B) was disulfonated, but the repeating unit (B) was not sulfonated. The water uptake of this sulfonated copolymer was measured after initially dry films of the copolymer (cast from a dimethylformamide solution) were immersed in water for 24 hours at room temperature. The water absorption amount obtained was 7.5% by weight. Example 7 (comparative example) Repeating unit (A) (ether bond para position in subunit)
The homopolymer (10 g) was dissolved in concentrated sulfuric acid (98% w/w) with stirring, and samples (50 ml) were taken over time and precipitated in dilute sulfuric acid or saturated sodium sulfate. Polymer samples corresponding to various sulfonation times were analyzed in dimethyl sulfoxide solution using 220MHz NMR spectroscopy, and the following properties were confirmed. 1 hour 85% of the units have −SO ₂ OH groups (Na
isolated as salt). 2 hours 99% of the units have −SO ₂ OH groups (Na
isolated as salt). 4.5 hours 100% of the units have _-SO2OH groups (isolated as Na salt). 23 hours 98% of the units have _-SO2OH groups (isolated as free acid). Virtually all subunits had one _-SO2OH group. Example 8 (comparative example) A homopolymer of repeating unit (A) (ether bond ortho position in the subunit) was sulfonated in concentrated sulfuric acid (98% W/W), and the product was prepared as a concentrated sulfuric acid solution.
Analyzed by 220MHz NMR spectroscopy (the product did not precipitate by pouring the acid solution into water). As in the case of the homopolymer of the repeating unit (A) above (ether bond para position in the subunit), this product has virtually all of the subunits in one -
It was observed that it was rapidly sulfonated to have an SO ₂ OH group. Example 9 (comparative example) Repeating unit (A) (ether bond meta position in subunit)
The homopolymer was sulfonated in concentrated sulfuric acid (98% W/W) and the product was analyzed as a solution in concentrated sulfuric acid (the product did not precipitate by pouring the acid solution into water) at 220MHz NMR spectroscopy. Analyzed by analytical method. Although it was observed that the product was rapidly sulfonated, as in the case of the homopolymer of repeating unit (A) (ether bond para or ortho position in the subunit) described above, in this example virtually all of the subunits were sulfonated. The unit had two _-SO2OH groups. Example 10 (Comparative Example) A homopolymer (50 g) containing the repeating unit (B) was dissolved in concentrated sulfuric acid (98% W/W) (200 ml), allowed to stand for 72 hours, precipitated in dilute sulfuric acid, and washed. , shredded and dried. Infrared and NMR spectra of the product confirmed that the product was the same as the starting material. Example 11 (comparative example) A homopolymer (20 g) containing repeating unit (B) was added to chlorosulfonic acid (100 ml). Slight bubbling was observed and white smoke was produced. After standing overnight (polymer residence time meter in chlorosulfonic acid
20 hours), add 300 ml of concentrated sulfuric acid (98% W/W) to this solution.
and this solution was then poured onto ice.
A very fine precipitate formed which was filtered off very slowly, washed once with water and then dried. The product appeared to be almost completely soluble in water, indicating that it was highly sulfonated. Example 12 (Comparative Example) Homopolymer (20 g) of repeating unit (B) was mixed with fuming sulfuric acid (150 ml) and left overnight. The resulting black solution still contained undissolved polymer, so it was stirred for an additional 5 hours and then poured into water. No precipitate was formed, but instead a brownish-orange solution was obtained. The product was assumed to be highly sulfonated or completely degraded and was discarded. In another experiment, the homopolymer (15 g) of the repeating unit (B) was dissolved in concentrated sulfuric acid (98% W/W), then fuming sulfuric acid (50 ml) was added, the solution was stirred for 30 minutes, It was then poured onto ice and left overnight. A gummy white solid precipitated and was washed and dried.
This product was confirmed to be highly sulfonated.

Claims (1)

[Scope of Claims] 1 Dihydroxyphenol selected from hydroquinone, catechol or resorcinol is combined with 4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone, and dihydroxyphenol and 4,4'-dihydroxydiphenyl sulfone. A repeating unit of formula (A) characterized in that it is condensed using 1 to 99 mol% of dihydroxyphenol based on the total amount of enylsulfone. 1 to 99 mol% and correspondingly repeating units of formula (B), A method for producing a polyarylethersulfone copolymer comprising 99 to 1 mol%. 2. The manufacturing method according to claim 1, wherein the dihydroxyphenol is 5 to 80 mol% of the total amount of dihydroxyphenol and 4,4'-dihydroxyphenyl sulfone. 3. The manufacturing method according to claim 1 or 2, wherein the dihydroxyphenol is hydroquinone. 4 Claims 1 to 3 in which the condensation is carried out using an alkali metal carbonate or bicarbonate
The manufacturing method according to any one of Items. 5. The manufacturing method according to any one of claims 1 to 4, wherein the condensation is carried out in the presence of a sulfone or a sulfoxide.