POLYARYLENE ETHER COPOLYMER

Abstract

A polyarylene ether copolymer comprising i) at least one block comprising in polymerized form A) isosorbide, isomannide, isoidide or a mixture thereof and B) at least one unit comprising at least one difunctional compound comprising at least one dichlorodiaryl sulfone, a dichlorodiaryl ketone or a mixture thereof and ii) at least one block comprising in polymerized form C) at least one polyalkylene oxide, 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 copolymer comprising i) at least one block comprising in polymerized form A) isosorbide, isomannide, isoidide or a mixture thereof and B) at least one unit comprising at least one difunctional compound comprising at least one dichlorodiaryl sulfone, a dichlorodiaryl ketone or a mixture thereof and ii) at least one block comprising in polymerized form C) at least one polyalkylene oxide.

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

3. The polyarylene ether block copolymer according to claim 1, comprising C) at least one polyethylene oxide.

4. The polyarylene ether copolymer according to claim 1, wherein the polyalkylene oxide has a number average weight of from 200 to 20 000 g/mol, determined by potentiometric titration using potassium hydroxide solution.

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

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

7. The polyarylene ether copolymer according to claim 1, comprising i) at least one block comprising in polymerized form at least one unit of the general formula I ##STR00007## 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—, —SO2-, S═O, C═O, —N═N—, and —CRaRb-, where Ra and Rb 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 —SO2- or —CO—, Z: a group derived from ISOSO, ISOMA or IS OID Ar and Ar.sup.1: independently of one another an arylene group having from 6 to 18 carbon atoms.

8. A process for the preparation of a polyarylene ether copolymer comprising reacting a) isosorbide, isomannide, isoidide or a mixture thereof and b) at least one difunctional compound comprising a dichlorodiaryl sulfone, a dichloodiaryl ketone or a mixture thereof with c) at least one polyalkylene oxide.

9. The process according to claim 8 comprising reacting the monomers in the presence of at least one polar aprotic solvent in the absence of an azeotrope forming compound.

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

11. The use according to claim 10 in the preparation of membranes.

12. A dope solution for the manufacture of membranes comprising at least one polyarylene ether copolymer according to claim 1.

13. A fiber comprising at least one polyarylene ether copolymer according to claim 1.

14. A membrane comprising at least one polyarylene ether copolymer according to claim 1.

15. An article comprising at least one membrane according to claim 13.

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

17. Use of the membrane according to claim 14 for the separation of gases.

Description

EXAMPLES

[0149] The examples below provide further explanation of the invention, but do not restrict the same.

Definitions and Abbreviations

[0150] Reaction time: time during which the reaction mixture was kept at 190° C. [0151] CA contact angle [0152] DCDPS: 4,4′-dichlorodiphenylsulfone [0153] DMAC: dimethylacetamide [0154] ISOSO: isosorbide [0155] NMP: N-methyl-2-pyrrolidone [0156] PEO polyethylene oxide [0157] PESU 1 polyarylene ether sulfone polymer with a viscosity number 84.0 ml/g, a Tg of 226° C. and a Mw of 75 000 GPC g/mol (in DMAC, polymethylmethacrylate standard) (Ultrason® E 6020 BASF SE) [0158] PVP: polyvinylpyrrolidone [0159] PEG: polyethylene glycole [0160] PWP pure water permeation [0161] MWCO molecular weight cut off

[0162] 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.

Isolation and Testing of the Copolymers

[0163] 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 I/h. The so obtained beads were then extracted with water at 85° C. for 20 h (water throughput 160 I/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 %.

[0164] 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)).

[0165] The content of isosobide and polyethylene oxide in the polyarylene ether copolymers was determined by .sup.1H-NMR analysis on a CDCl.sub.3 solution.

[0166] The Tg of the copolymers was determined by DSC-measurement with a heating rate of 10 k/min in the second heating process.

[0167] 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 hours. 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.

Examples 1 to 4 According to the Invention—Preparation of Polyarylene Ether Copolymers and Comparative Example C1—Preparation of a Polyarylene Ether

General Procedure:

[0168] In a vessel equipped with a stirrer, Dean-Stark-trap, nitrogen-inlet and temperature control, DCDPS, ISOSO, (and if present) PEO and potassium carbonate (volume average particle size of 9.5 μm) were suspended under nitrogen atmosphere in 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). The amounts and materials employed as well as the properties are given in Table 2 below:

TABLE-US-00002 TABLE 2 Examples 1 2 3 4 C1 DCDPS [g] 580.063 580.063 580.063 580.063 435.047 [mol] 2.02 2.02 2.02 2.02 1.515 ISOSO [g] 283.43 283.50 286.43 283.50 219.21 [mol] 1.96 1.94 1.96 1.94 1.50 PEO Mn [g/mol] 998 998 2010 2010 Not used [g] 39.92 59.88 80.04 120.60 [mol] 0.04 0.06 0.04 0.06 K.sub.2CO.sub.3 [g] 304.052 304.052 304.052 304.052 269.51 [mol] 2.20 2.20 2.20 2.20 1.95 NMP [ml] 1050 1050 1050 1050 790 Reaction time [h] 9 9 9 9 14 Properties V.N. [ml/g] 35.2 37.2 36.6 38.1 33.6 Theoretical Isosorbid 38.1 36.5 35.8 33.8 40.2 cont. [wt. %] Amount ISOSO.sup.a) [wt %] 36.9 35.8 35.3 33.3 37.4 Rate of incorporation of 96.9 98.1 98.7 98.4 93.0 ISOSO Amount PEO.sup.a) [wt %] 5.0 7.4 9.8 13.9 — Tg [° C.] 235 226 221 217 243 CA [°] 69 65 61 57 76 .sup.a)as found in the polyarylene ether copolymer

[0169] The ISOSO comprising polyarylene copolymers according to this disclosure had higher viscosity numbers and the contact angle was lower than the ISOSO comprising polyarylene ether C1 prepared under comparative conditions. The reaction proceeded faster for the ISOSO comprising polyarylene copolymers according to this disclosure. In addition, the rate of incorporation of the ISOSO was higher.

Examples Preparation of Membranes

Preparation of the Casting Solution as Well as the Membrane:

[0170] Into a vessel equipped with a stirrer, nitrogen-inlet and thermometer 390 ml of NMP, 25 g of PVP (Luvitec® K40) and 50 g of PESU 1 as well as 35 g of the respective polyarylene ether copolymer according to the invention 1 to 4 or the polymer C1.

[0171] The mixture was heated under gentle stirring at 60° C. until a homogeneous clear viscous solution was obtained. The time to achieve the clear solution was monitored (see Table 3).

[0172] The solution was then degassed overnight at room temperature. After that the membrane solution was reheated at 60° C. for 2 hours and casted onto a glass plate with a casting knife (300 microns) at 60° C. using an Erichsen Coating machine operating at a speed of 5 mm/min. The membrane film was allowed to rest for 30 seconds before immersion in a water bath at 25° C. for 10 minutes.

[0173] After the membrane had detached from the glass plate, the membrane was carefully transferred into a water bath for 12 h. Afterwards the membrane was transferred into a bath containing 2500 ppm NaOCl at 50° C. for 4.5 h to remove PVP. After that process the membrane was washed with water at 60° C. and the one time with a 0.5 wt.-% solution of sodium bisulfite to remove active chlorine. After several washing steps with water the membrane was stored wet until characterization started.

[0174] In most cases a flat sheet continuous film with micro structural characteristics of UF membranes having dimension of at least 10×15 cm size is obtained. The membrane presents a top thin skin layer (1-3 microns) and a porous layer underneath (thickness: 100-150 microns).

Membrane Characterization

[0175] Using a pressure cell with a diameter of 60 mm, the PWP of the membranes was tested using ultrapure water (salt-free water, filtered by a Millipore UF-system). In a subsequent test, a solution of different PEG-Standards covering the molecular weight (Mw) range from 1000 to 1.000.000 g/mol, concentration of PEG/PEO 0.1 wt. % in water, was filtered at a pressure of 0.15 bar. By GPC-measurement of the feed and the permeate, the molecular weight cut-off was determined. For the GPC-measurements the solutions were used as obtained/prepared. The GPC-measurements were run at 35° C. using two columns with hydroxylated PMMA as stationary phase and a RI-detection system at a flow rate of 0.8 ml/min.

[0176] The composition of the solution and the results are given in Table 3.

TABLE-US-00003 TABLE 3 Amount in [wt %] MC1* M1** M2** M3** M4** MC2* PESU 1 10 10 10 10 10 17 Copolymer 1 7 Copolymer 2 7 Copolymer 3 7 Copolymer 4 7 Polymer C1 7 — PVP 5 5 5 5 5 5 NMP 78 78 78 78 78 78 Time to 3.95 3.2 3.0 2.86 2.75 4.25 dissolve [h] PWP 530 680 720 780 880 510 [l/m2 * h * bar] MWCO [kD] 57 56 53 56 59 59 *Comparative Membranes **Membranes according to this disclosure

[0177] Membranes prepared from the polyarylene ether copolymers comprising ISOSO showed a higher permeability than those of the polyarylene ether C1 at comparative separation properties. The dope-solutions comprising the polyarylene ether copolymers according to this disclosure could be prepared in shorter time.