JPS5974128A - Polyaryl ether sulfon copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to polyarylether sulfone copolymers.

We have shown that a polyarylether sulfone polymer having only repeating units of the formula dissolves in concentrated sulfuric acid (98% w/w) and sulfonates very rapidly to yield a completely water-soluble product. I found it. This is likely due to the substitution of -5O20H groups on all or most of the aromatic rings of the subunit of the polymer (see Examples 7-9), placed in the ortho or para position in said subunit. This may be due to monosulfonation, which occurs in the case of polymers with ether bonds, and disulfonation, which occurs in the case of polymers with ether bonds located in the meta position of the subunit.

In contrast, we have found that polyarylether sulfones having only repeating units of formula ( ) undergo virtually no sulfonation in concentrated sulfuric acid (98% W/W). However, other sulfonating agents, such as oleum and chlorosulfonic acid, and even mixtures of concentrated sulfuric acid and small amounts of oleum, do not change the polymer (see Example 10). also completely sulfonates and/or decomposes the above polymer (see Examples 11 and 12). Therefore, the polyaryl ether sulfone copolymer (/i concentrated sulfuric acid (98
controlled sulfonation in 10 W/W) to give hydrophilic sulfonated copolymers (ranging in size up to a fully water-soluble polymer) by varying the proportion of repeating units in the copolymer. .

Structure of the invention According to the invention, repeating units of formula (6), 1 to 99 mol%
, preferably 5 to 80 mol %, and correspondingly 99 to 1 mol %, preferably 95 to 20 mol % of repeating units of formula (1). is provided.

The repeating unit preferably has an ether bond located at the para position, and is preferably represented by the following formula.

The polyaryl ether sulfone copolymer of the present invention contains substantially all of the copolymerized units (5) after sulfonation! 1
The 111 position is sulfonated and controlled sulfonation as described above such that substantially all of the units remain in the non-sulfonated state after sulfone death to produce a hydrophilic sulfonated copolymer. be able to.

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 at room temperature up to complete solubility in water.

Sulfonated hydrophilic copolymers derived from the copolymers of the invention (preferably 2 to 40% by weight of water at room temperature,
more preferably 5 to 60% water by weight), because they are not only characterized by hydrophilicity but also have considerable strength even when containing significant amounts of water (e.g. up to 20% water). (see Example 5), membrane material,
For example, it is potentially useful as a membrane material for ultrafiltration processes such as desalination and microbial removal.

Ionomers of these sulfonated copolymers sulfonated with -8020H groups, for example,
0. It can be easily prepared by converting it into a salt such as '-M+ (M is an alkali metal or NR4°R is an alkyl group). These also have uses as hydrophilic polymers. Therefore, the sulfonyl group of the sulfonated copolymer derived from the copolymer of the present invention has the formula-8
O20Y [in the formula, Y is H.

Those having an alkali metal or NR4 (R represents an alkyl group) are preferred.

A copolymer having the repeating units (- and (-)) can be prepared using a suitable dihydroxyphenol (e.g. hydroquinone) in the presence of a sulfone or sulfoxide solvent using the method for preparing polyarylene polyethers described in Canadian Patent No. 847,965. , catechol or resorcinol), 4,4'-dihydroxydipheny/lz sulfone and 4,4'-dichlorodiphenyl sulfone and an alkali metal carbonate or bicarbonate.

Example The invention is illustrated by the following examples.

Example 1 Copolymer (degree (5) 25
Mol%~66.7mol%, therefore unit ■75mol%~5
6.5 mol%) was reacted with appropriate 5 parts of hydroquinone and 4,4'-dihydroxydiphenylsulfone in the presence of KCO using diphenylsulfone as the polymerization solvent. It was prepared by Polymerization temperature is 200~
The temperature was within the range of 290°C. Substantially equimolar components of total bisphenol and cybaride were used with 2CO3 in a molar equivalent excess of slightly more than two times the molar equivalent of cybaride.

The copolymer was sulfonated as follows (a copolymer of 25 mol% (A)/5 mol% of FO3Jy was used as a typical example).

Copolymer (209) was dissolved in concentrated sulfuric acid (98% W/W) (110
tnl) for 18 hours to obtain a very viscous solution. Additional concentrated sulfuric acid (50 g) was added and shaking continued for an additional 18 hours (ie, 66 hours total). This solution was then poured into distilled water (800*) in a Waring prefecture, resulting in a white precipitate. This white precipitate was filtered and washed with fresh water in a burengu for 3 minutes, with filtration separation after each wash.
Washed twice. The product was dried overnight in a vacuum oven at about 65°C.

All sulfonated copolymers ij: 220 MHzNM
Analysis by R spectroscopy showed that substantially all of the sub-repeat units of the polymer chain were monosulfonated, but none of the repeat units (■) were sulfonated.

All sulfonated products were soluble in dimethylformamide and dimethylsulfoxide.

Example 2 A copolymer containing 80 mol % of anti-commercial prisoners (ether bond para position of subunits) and 80 mol % of units (B) was prepared as described in Example 1. Sample (5
1) with concentrated sulfuric acid (98% W/W) (20ηIe) -
Toshita Kusabe. Concentrated sulfuric acid (20 rnl) was added to the mixture and the incubation was continued for an additional 24 hours. This solution was then poured into distilled water in a Waring Prengu to cause scuttling. The white precipitate was filtered, washed four times with water, and dried in a vacuum oven overnight. Repeating unit (8) (ether bond of subunit) (U) and (B), respectively, ■ 5 mol 0
6/□□□95 mol%, (A10 mol%/@90 mol%
, (A) 20 mol%/@80 mol% and 40 mol%/
The amount of the starting copolymer and the amount of concentrated sulfuric acid used are different, but the above copolymer (A) 80
0 mol %/■ 20 mol % was used to form 7-rehon.

Analysis of the sulfonated product by 220 MHz spectroscopy reveals that substantially all of the subrepeat units of the resulting polymer chain are monosulfonated.

It was shown that no sulfonation had occurred in any of the repeating units (■).

Example 3 (Example of use) Add excess N to the sulfonated copolymer of Example 2.
Prepared by neutralization in aOH solution. Neutralization of the sulfonated (8) 10 mol %/(13) 90 mol % copolymer will be explained as a representative example.

Sulfonation (8) of Example 2 10 mol%/cBJ 90 mol%
Copolymer (50?) in water (600, m6) with Na0H (
30f) Stir in solution overnight. Next, mix this mixture with 6
Heated to 0-80°C throughout the day and cooled to 40°C. The product was filtered, washed four times with water and dried in an oven.

Sulfonation (A) 10 mol o10/(f3) 90 mol%, (5) 20 mol%/(I180 mol% and HGA)
The sodium content of the 4o mol%/■60 mol% copolymer was measured using flame emission spectroscopy (L"ES) and NMR spectroscopy shows that all units (5) are monosulfonated. The results were as follows.

10/90 0.53% 0.58%2 [1
/ 811 1.20% 1. OO'/.

40/60 2.30% 2.06% The water absorption before and after sulfonation of the copolymer of Example 2 and the water absorption of the neutralized sulfonated copolymer of Example 6 were determined by comparing the dry film of the copolymer (dimethylformamide solution). first cast at room temperature for 24 hours.
Measurements were taken after soaking in water for an hour. The results were as follows.

5/95 2.4 4.5 2.4
10/90 2.5 4.4 3.
620/80 2.3 4.5 5
．． 54o/6o '5.98.9 13
．． 180/20 Not measured Not measured 6
6.6 Example 5 (Useful example) The mechanical properties of the sulfonated (8) 40 mol%/()3) 60 mol% and (A) 80 mol%/(B1 20 mol%) copolymers of Example 2 were The rolled film was tested in the dry state and after water absorption.For comparison, the unit
A homopolymer containing only (non-sulfonated) was also tested. The results were as follows.

Line wetness 1.0 1350 - -Example 6 Copolymer (5? ) was prepared essentially according to the procedure described in Example 1 (using resorcinol as a substitute for hydroquinone). This copolymer 51i' was dissolved in concentrated sulfuric acid (98% W/W) and left for 36 hours.

This solution was poured into distilled water to cause scuttling. The white precipitate was filtered, washed three times with water, and oven dried. The product was analyzed by 220 MHz spectroscopy;
It was confirmed that substantially all of the secondary repeating units in the produced polymer chain were disulfonated, but the repeating unit (■) was not sulfonated.

The water absorption of this sulfonated copolymer was measured after initially dry films of the copolymer (cast from a dimethylformamide solution) were soaked in water for 24 hours at room temperature. The amount of water absorbed was 15% by weight.

Example 7 (ratio example) Concentrated sulfuric acid (98% W
/W) and samples (50 ml) were removed over time and precipitated in dilute sulfuric acid or saturated sodium sulfate. Polymer samples corresponding to various sulfonation times were prepared in dimethyl sulfoxide solution at 220 MHz.
It was analyzed by NMR spectroscopy and confirmed to have the following properties.

1 hour 85% of the units have 18O20H groups (N
isolated as a salt).

2 hours 99% of the units have 18O20H groups (
isolated as Na salt).

4.5 hours 100% of the units have 18O20H groups (isolated as Na salts).

23 hours 98% of the units have 18o, 20H groups (isolated as free acid).

Virtually all subunits had one -8O20H group.

Example 8 (Comparative Example) A homopolymer of repeating unit (5) (ether bond ortho position in the subunit) was sulfonated in concentrated sulfuric acid (98% W/W)7, and the product was dissolved in concentrated sulfuric acid at 220 MHz NM.
Analyzed by R spectroscopy (the product did not precipitate by pouring the acid solution into water). The above repetition unit (
As in the case of a homopolymer of ~ (ether bond para position in the subunit), this product has virtually all of the subunits -
It was observed that the compound was rapidly sulfonated to have a -5O20H group.

Example 9 (Comparative Example) A homopolymer of repeating unit (5) (ether bond meta position in the subunit) was sulfonated in concentrated sulfuric acid (98% W/W) and the product was dissolved in concentrated sulfuric acid (this The product did not precipitate by pouring the acid solution into water)22
Analyzed by 0 MHz NMR spectroscopy.

Although we observed that the product was rapidly sulfonated, as in the case of the homopolymer of repeating unit (5) (ether bond para or ortho position in the subunit) described above, in this example virtually all of the subunits were The unit (d) had two -5O20H groups.

Example 10 (comparative example) A homopolymer (50r) containing repeated hijiitadashi was mixed with concentrated sulfuric acid (9
8% W/W) (200n/), left for 72 hours, precipitated in dilute sulfuric acid, washed, shredded,
Dry. Infrared and NMR spectra of the product confirmed that the product was the same as the starting material.

Example 11 (Comparative Example) A homopolymer (20f) containing repeating units (b) was added to chlorosulfonic acid (100 yd). There was slight foaming and white fumes. - After standing overnight (total residence time of polymer in chlorosulfonic acid 20 hours), this solution was mixed with 600 ml of concentrated sulfuric acid (98% W/W). Pour it inside;
This solution was then poured onto ice. A very fine precipitate formed which was filtered 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) A homopolymer (20r) of repeating units (b) was mixed with fuming sulfuric acid (
150 mA) and set it up 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, a homopolymer (14
M') was dissolved in concentrated sulfuric acid (98% W/W), then fuming sulfuric acid (50 m7) was added and the solution was stirred for 60 min.
It was then poured over ice and left overnight. A gummy white solid precipitated and was washed and dried. This product was confirmed to be highly sulfonated.

Margin below

Claims (1)

[Scope of Claims] 1. A polyarylethersulfone copolymer comprising 1 to 99 mol% of a repeating unit of formula (b) and 99 to 1 mol% of a corresponding repeating unit of formula (b). Combined. 2. The polyarylethersulfone copolymer according to claim 1, comprising 5 to 80 mol% of repeating units (A) and correspondingly 195 to 20 mol% of repeating units (f3). 3. Units ( The polyarylethersulfone copolymer according to claim 1 or 2, wherein 戊 is represented by the formula.