POLYARYLENE ETHER SULFONE

Abstract

A polyarylene ether sulfone comprising in polymerized form A) isosorbide, isomannide, isoidide or a mixture thereof and B) at least one at least one nonsulfonated dihalodiaryl sulfone (compound B) and C) at least one sulfonated dihalodiaryl sulfone (compound C), a process for its preparation and its use in the preparation of coatings, films, fibers, foams, membranes or molded articles.

Claims

1. A polyarylene ether sulfone comprising in polymerized form A) isosorbide, isomannide, isoidide or a mixture thereof and B) at least one at least one nonsulfonated dihalodiaryl sulfone (compound B) and C) at least one sulfonated dihalodiaryl sulfone (compound C).

2. The polyarylene ether sulfone according to claim 1, comprising A) isosorbide.

3. The polyarylene ether sulfone according to claim 1, comprising from 20 to 99 mol-% of compound B and from 1 to 20 mol-% of compound C, based on the sum of the mol-% of compounds B and C.

4. The polyarylene ether sulfone according claim 1 wherein compound C is 4,4′-dichlorodiphenylsulfone-3,3′-disulfonic acid or 4,4′-dichlorodiphenylsulfone-3,3′-disulfonic acid disodium salt or a mixture thereof.

5. The polyarylene ether sulfone according to claim 1, comprising in polymerized form E) at least one tri- or higher functional monomer.

6. The polyarylene ether sulfone according to claim 5, comprising E) at least one triol.

7. The polyarylene ether sulfone according to claim 5, comprising E) 1,1,1-trishydroxyphenyl ethane.

8. The polyarylene ether sulfone according to claim 1, comprising in polymerized form at least one unit of the general formula (I) ##STR00006## where the definitions of the symbols t, q, Q, T, Y, Ar and Ar.sup.1 are as follows: r: 0, or 1 t, q: independently of one another 0, or 1, or 2, or 3, Q, T, Y: independently of one another in each case a chemical bond or group selected from —O—, —S—, —SO.sub.2—, S═O, C═O, —N═N—, and —CR.sup.aR.sup.b—, where R.sup.a and R.sup.b independently of one another are in each case a hydrogen atom or a C1 to C12-alkyl, C1 to C12-alkoxy, C3 to C12-cycloalkyl, or C6 to C18-aryl group, and where at least one of Q, T, and Y is —SO.sub.2— or —CO—, Z: a group derived from isosorbide, isomannide, isoidide Ar and Ar.sup.1: independently of one another an arylene group having from 6 to 18 carbon atoms.

9. A process for the preparation of a polyarylene ether sulfone comprising reacting a) isosorbide, isomannide, isoidide or a mixture thereof and b) at least one nonsulfonated dihalodiaryl sulfone, with c) at least one sulfonated dihalodiaryl sulfone.

10. The process according to claim 9 comprising reacting the monomers in the presence of a polar aprotic solvent in the absence of an azeotrope forming compound.

11. Use of a polyarylene ether sulfone according to claim 1 in the preparation of coatings, films, fibers, foams, membranes or molded articles.

12. The use according to claim 11 in the preparation of membranes.

13. A fiber comprising a polyarylene ether sulfone according to claim 1.

14. A membrane comprising a polyarylene ether sulfone according to claim 1.

15. An article comprising a membrane according to claim 14.

16. Use of the membrane according to claim 14 in contact with water, a body fluid or a liquid in food production.

Description

EXAMPLES

[0144] The examples below provide further explanation of the invention, but do not restrict the same.

Definitions and Abbreviations

[0145] Reaction time: time during which the reaction mixture was kept at 190° C.

[0146] CA contact angle

[0147] DCDPS: 4,4″-dichlorodiphenylsulfone

[0148] sDCDPS disodium diphenylsulfone-4,4″-dichloro-3,3″-disulfonate

[0149] BP: 4,4″-dihydroxybiphenyl

[0150] ISOSO: isosorbide

[0151] NMP: N-methyl-2-pyrrolidone

[0152] The particle size of the potassium carbonate was determined at a suspension of the solid in chlorobenzene/sulfolane 60/40 using a Malvern Mastersizer 2000 instrument.

[0153] Isolation and Testing of the Copolymers

[0154] The copolymers obtained were isolated by dividing the filtrated reaction mixture into droplets and transferring the droplets into a precipitation bath. The precipitation solvent was desalinated water at room temperature. The precipitation height was 0.5 m. The throughput was appr. 2.5 l/h. The so obtained beads were then extracted with water at 85° C. for 20 h (water throughput 160 l/h). Thereafter the beads were dried under reduced pressure at a temperature below the glass transition temperature (Tg) to a residual moisture of less than 0.5 wt %.

[0155] The solution viscosity (V.N.) was determined using a solution of 0.01 g/ml polymer in NMP at 25° C. (DIN EN ISO 1628-1 (October 2012)).

[0156] The content of isosorbide and sDCDPS in the polyarylene ether sulfone was determined by .sup.1H-NMR analysis on a CDCl.sub.3 solution.

[0157] The Tg of the copolymers was determined by DSC-measurement with a heating rate of 10 k/min in the second heating process.

[0158] The contact angle (CA) of the polymers were measured against water on the respective polymer films, which were manufactured from a 25 wt % solution in NMP. The films were dried under reduced pressure at 80° C. for 48° C. The measurements were carried out at 23° C. with a DSA 100 analyzer (from Krüss GmbH). The values given in Table 2 are average values from 10 measurements.

[0159] The viscosity of the spinning solution was measured with a Brookfield rheometer at 60° C. at at 20 rpm using solutions having the following composition:

TABLE-US-00003 19 wt-% nonsulfonated polyarylene ether respectively polyarylene ether sulfone  6 wt-% polyvinylpyrrolidone K90 (Luvitec ® powder from BASF SE) 75 wt-% NMP

Examples 1 to 7 According to the Disclosure—Preparation of Polyarylene Ether Sulfones and Comparative Example C1 and C2—Preparation of a Nonsulfonated Polyarylene Ethers

[0160] General Procedure:

[0161] In a vessel equipped with a stirrer, Dean-Stark-trap, nitrogen-inlet and temperature control, DCDPS, ISOSO, (and if present) sDCDPS, BP and potassium carbonate (volume average particle size of 33.2 μm) were suspended under nitrogen atmosphere in 1050 ml NMP. Under stirring the mixture was heated up to 190° C. within one hour. The water that was formed in the reaction was continuously removed by distillation. Potential solvent loss to be accounted for was monitored. Nitrogen is purged through the mixture and the mixture is kept at 190° C. for the reaction time. After this time 1950 ml NMP were added to cool down the mixture to room temperature (within one hour) under nitrogen. To remove the potassium chloride formed the reaction mixture was filtrated. The obtained polymer solution was then precipitated in water, the resulting polymer beads were separated and then extracted with hot water (85° C.) for 20 h. Then the beads were dried at 120° C. for 24 h at reduced pressure (<100 mbar).

[0162] The amounts and materials employed as well as the properties are given in Tables 2 and 3 below.

[0163] The polyarylene ether sulfones according to this disclosure had lower solution viscosity in the spinning solution than the non-sulfonated polyarylene ethers. Thus, they were easier to process. They were suitable for the manufacture of membranes. Also, the polyarylene ether sulfone according to this disclosure had a higher Tg and a lower contact angle than ISOSO-free sulfonated polyarylene ether sulfone. In addition, the examples show that the viscosity number drops if more than 20 mol-% of s-DCDPS is used.

TABLE-US-00004 TABLE 2 Examples C1 1 2 C2 3 4 C3 5 6 C4 7 C5 DCDPS [g] 574.34 559.96 545.60 574.34 559.96 545.60 574.34 559.96 545.60 545.60 488.17 445.10 [mol] 2.00 1.95 1.90 2.00 1.95 1.90 2.00 1.95 1.90 1.90 1.70 1.55 sDCDPS [g] Not 24.563 49.12 Not 24.563 49.12 Not 24.563 49.12 49.12 147.38 221.06 [mol] used 0.05 0.10 used 0.05 0.10 used 0.05 0.10 0.10 0.3 0.45 ISOSO [g] 73.07 73.07 73.07 146.14 146.14 146.14 219.21 219.21 219.21 Not 73.07 73.07 [mol] 0.50 0.50 0.50 1.00 1.00 1.00 1.50 1.50 1.50 used 0.50 0.50 BP [g] 279.32 279.32 279.32 186.21 186.21 186.21 93.11 93.11 93.11 372.42 279.32 279.32 [mol] 1.50 1.50 1.50 1.00 1.00 1.00 0.50 0.50 0.50 2.00 1.50 1.50 K2CO3 [g] 304.052 304.052 304.052 317.88 317.88 317.88 331.70 331.70 331.70 293.00 304.0 304.0 [mol] 2.20 2.20 2.20 2.30 2.30 2.30 2.40 2.40 2.40 2.12 2.20 2.20

TABLE-US-00005 TABLE 3 Examples C1 1 2 C2 3 4 C3 5 6 C4 7 C5 Properties V.N. [ml/g] 70.9 68.5 67.9 68.7 67.9 68.8 68.0 69.1 69.2 83.2 65.6 41.5 Amount 23.5 24.0 24.0 48.9 48.7 47.9 74.3 74.2 74.3 — 23.9 23.7 ISOSO [mol %] Amount — 2.2 4.7 — 2.3 4.6 — 2.2 4.6 4.7 14.5 21.8 sDCDPS [mol %] Tg [° C.] 229 232 236 234 237 240 239 241 244 227 240 242 CA [°] 75 62 51 76 63 51 76 63 52 62 43 37 η [Pa*s] 24.6 23.1 20.1 29.0 26.5 24.3 31.0 28.7 27.1 32.1 20.4 21.5