POLYARYLENE ETHER

Abstract

A polyarylene ether comprising in polymerized form A) at least one tri- or higher functional compound and B) isosorbide, isomannide, isoidide or a mixture thereof, wherein the polyarylene ether is a polyarylene ether sulfone or a polyarylene ether ketone, a process for its preparation and its use in the preparation of a coating, film, fiber, foam, membrane or molded article.

Claims

1. A polyarylene ether comprising in polymerized form A) at least one tri- or higher functional compound and B) isosorbide, isomannide, isoidide or a mixture thereof, wherein the polyarylene ether is a polyarylene ether sulfone or a polyarylene ether ketone.

2. The polyarylene ether according to claim 1, comprising A) at least one trifunctional compound.

3. The polyarylene ether according to claim 1, comprising A) at least one triol.

4. The polyarylene ether according to claim 1, comprising A) 1,1,1-trishydroxyphenyl ethane.

5. The polyarylene ether according to claim 1, comprising B) isosorbide.

6. The polyarylene ether according to claim 1, comprising diol C1) at least one compound having two hydroxy groups and which is not compound B.

7. The polyarylene ether according to claim 1, comprising A) from 0.5 to 5 mol %, based on the total amount of compounds A and B and diol C1 comprised in the polyarylene ether at least one tri- or higher functional compound.

8. The polyarylene ether according to claim 1, comprising at least one unit of the general formula II ##STR00006## where the definitions of the symbols t, q, Q, T, Y, Ar and Ar.sup.1 are as follows: t, q: independently of one another 0, 1, 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 C.sub.1-C.sub.12-alkyl, C.sub.1-C.sub.12-alkoxy, or C.sub.6-C.sub.18-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, and 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 comprising reacting a) at least one tri- or higher functional compound and b) isosorbide, isomannide, isoidide or a mixture thereof with c) a difunctional compound comprising at least one dichlorodiaryl sulfone, a dichlorodiarylketone or a mixture thereof.

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 according to claim 1 in the preparation of a coating, film, fiber, foam, membrane or molded article.

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

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

14. A membrane comprising the polyarylene ether according to claim 1.

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

16. The article according to claim 15 in contact with water, a body fluid or a liquid in food production.

Description

EXAMPLES

[0120] The examples below provide further explanation of the invention, but do not restrict the same.

Definitions and Abbreviations

[0121] Reaction time: time during which the reaction mixture was kept at 190° C.

DCDPS: 4,4′-dichlorodiphenylsulfone
DHDPS 4,4′-dihydroxydiphenylsulfone
BP: 4,4′-dihydroxybiphenyl
ISOSO: isosorbide
THPE 1,1,1-trishydroxyphenylethan
NMP: N-methyl-2-pyrrolidone
PVP: polyvinylpyrrolidone
PEG: polyethylene glycole
PWP pure water permeation
MWCO molecular weight cut off

[0122] 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 as described above.

Examples C1 to 16: Preparation of Polyarylene Ethers

General Procedure

[0123] In a vessel equipped with a stirrer, Dean-Stark-trap, nitrogen-inlet and temperature control the monomers and for the experiments according to the invention also THPE, and potassium carbonate 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 loss of solvent to be accounted for was monitored. Nitrogen is purged through the mixture and the mixture is kept at 190° C. for the condensation time. After this time NMP was 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).

Comparative Example C1

[0124] The preparation was carried out according to the general procedure with the following specifics:

580.06 g (2.02 mol) of DCDPS, 292.28 g (2.00 mol) of ISOSO, 304.05 g (2.20 mol) of potassium carbonate (volume average particle size of 32.4 μm) were suspended in 1050 ml NMP.
Condensation time: 9 hours
1950 ml NMP were added to cool down the mixture.

Comparative Example C2

[0125] The preparation was carried out according to the general procedure with the following specifics:

435,047 g (1.515 mol) of DCDPS, 219.21 g (1.50 mol) of ISOSO and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 790 ml NMP.
Condensation time: 14 hours
1460 ml NMP were added to cool down the mixture.

Experiment 3 According to the Invention

[0126] The preparation was carried out according to the general procedure with the following specifics:

435,047 g (1.515 mol) of DCDPS, 212,852 g (1.4565 mol) of ISOSO, 9.19 g (0.03 mol) of THPE, 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 790 ml NMP.
Condensation time: 13 hours
1460 ml NMP were added to cool down the mixture.

Example 4 According to the Invention

[0127] The preparation was carried out according to the general procedure with the following specifics:

435,047 g (1.515 mol) of DCDPS, 210,441 g (1.44 mol) of ISOSO, 12,254 g (0.04 mol) of THPE and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 790 ml NMP.
Condensation time: 13 hours
1460 ml NMP were added to cool down the mixture.

Comparative Example C5

[0128] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 219.21 g (1.50 mol) of ISOSO, 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 790 ml NMP.
Condensation time: 14 hours
1460 ml NMP were added to cool down the mixture.

Comparative Example C6

[0129] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 219.21 g (1.50 mol) of ISOSO, 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP.
Condensation time: 14 hours
1600 ml NMP were added to cool down the mixture to room temperature

Comparative Example C7

[0130] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 153.48 g (1.05 mol) of ISOSO, 112.63 g (0.45 mol) of DHDPS, 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP
Condensation time: 14 hours
1600 ml NMP were added to cool down the mixture.

Comparative Example C8

[0131] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 175.37 g (1.20 mol) of ISOSO, 75.08 g (0.3 mol) of DHDPS, 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP.
Condensation time: 14 hours
1600 ml NMP were added to cool down the mixture.

Example 9

[0132] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 153.48 g (1.05 mol) of ISOSO, 101.36 g (0.405 mol) of DHDPS, 9.19 g (0.03 mol) of THPE, 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP.
Condensation time: 11 hours
1600 ml NMP were added to cool down the mixture.

Example 10

[0133] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 175.37 g (1.20 mol) of ISOSO, 63.82 g (0.255 mol) of DHDPS, 9.19 g (0.03 mol) of THPE, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP.
Condensation time of 12 hours
1600 ml NMP were added to cool down the mixture.

Comparative Example C11

[0134] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 218.18 g (1,493 mol) of ISOSO, 1.37 g (0.0045 mol) of THPE and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP.
Condensation time: 14 hours
1600 ml NMP were added to cool down the mixture.

Comparative Example C12

[0135] The preparation was carried out according to the general procedure with the following specifics:

432.91 g (1.5075 mol) of DCDPS, 201.67 g (1.38 mol) of ISOSO, 24.51 g (0.08 mol) of THPE and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size of 8.7 μm) were suspended in 650 ml NMP.
Condensation time: 14 hours
1600 ml NMP were added to cool down the mixture.

[0136] The results of these experiments are shown in Table 1.

Comparative Example C13

[0137] The preparation was carried out according to the general procedure with the following specifics:

577.16 g (2.01 mol) of DCDPS, 146.14 g (1.00 mol) of ISOSO, 186.21 g (1.00 mol) of BP and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size of 32.7 μm) were suspended in 1050 ml NMP.
Condensation time: 11 hours
1500 ml NMP were added to cool down the mixture.

Comparative Example C14

[0138] The preparation was carried out according to the general procedure with the following specifics:

577.16 g (2.01 mol) of DCDPS, 204.59 g (1.40 mol) of ISOSO, 111.73 g (0.60 mol) of BP and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size of 32.7 μm) were suspended in 1050 ml NMP.
Condensation time: 13 hours
1500 ml NMP were added to cool down the mixture.

Example 15 According to the Invention

[0139] The preparation was carried out according to the general procedure with the following specifics:

577.16 g (2.01 mol) of DCDPS, 146.14 g (1.00 mol) of Isosorbide, 175.04 g (0.94 mol) of BP, 12.25 g (0.04 mol) of THPE and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size of 32.7 μm) were suspended in 1050 ml NMP.
Condensation time: 6 hours
1500 ml NMP were added to cool down the mixture.

Example 16 According to the Invention

[0140] The preparation of was carried out according to the general procedure with the following specifics:

577.16 g (2.01 mol) of DCDPS, 204.59 g (1.40 mol) of ISOSO, 100.55 g (0.54 mol) of BP, 12.25 g (0.04 mol) of THPE and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size of 32.7 μm) were suspended in 1050 ml NMP.
Condensation time: 7.5 hours
1500 ml NMP were added to cool down the mixture.

[0141] The results of these experiments are shown in Table 2.

Isolation and Testing of the Polyarylene Ethers

[0142] The polymers 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 %.

[0143] 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)).

[0144] The content of isosorbide and the trishydroxy-phenyl ethane in the polyarylene ether was determined by .sup.1H-NMR analysis on a CDCl.sub.3 solution.

[0145] The Tg of the polymers was determined by DSC-measurement with a heating rate of 10 k/min in the second heating process.

[0146] The viscosity of the membrane dope solutions was measured with a Brookfield rheometer at 60° C. at 20 rpm using solutions having the following composition: 19 wt % of the respective poymer, 6 wt % polyvinylpyrrolidone (Luvitec K90, BASF SE) and 75 wt % NMP.

TABLE-US-00002 TABLE 1 Example C1* C2* 3** 4** C5* C6* C7* C8* 9** 10** C11** C12** V.N. 14.8 34.7 55.6 63.4 32.4 35.9 54.2 45.1 64.2 62.7 36.2 39.1 [ml/g] Content 36.8 37.6 36.6 37.7 37.5 37.3 24.8 29.0 25.8 29.9 37.3 34.5 Isosorbide [wt %] Isosorbide 92.1 93.5 94.2 98.2 92.8 92.4 95.3 94.9 98.9 97.5 92.9 94.0 incorp. Rate [%] Cl/OH− 1.01 1.01 1.009 1.01 1.005 1.005 1.005 1.005 1.005 1.005 1.005 1.005 ratio Time.sup.a) 9 14 13 13 14 14 14 14 11 12 14 14 [h] Tg [° C.] — 244 248 249 243 245 236 239 240 243 241 242 Yield <85 85.4 88.9 91.5 85.1 86.0 87.1 87.2 92.7 92.5 86.4 91.0 η [Pa*s] 4.3 19.0 20.8 21.7 17.5 18.6 28.2 24.1 22.0 22.6 15.4 14.6 *Comparative examples **Branched polyarylene ethers comprising ISOSO groups .sup.a)Condensation Time

TABLE-US-00003 TABLE 2 Example C13* C14* 15** 16** V.N. 65.0 47.7 75.1 73.9 [ml/g] Content 18.2 25.7 18.6 26.5 Isosorbide [wt %] Isosorbide 95.0 94.2 97.5 97.0 incorp. Rate [%] Cl/OH− 1.005 1.005 1.005 1.005 ratio Time.sup.a) 11 13 6 7.5 [h] Tg [° C.] 233 240 234 241 Yield 91.2 90.2 95.2 94.1 η [Pa*s] — — — — *Comparative examples **Branched polyarylene ethers comprising ISOSO groups .sup.b) Condensation Time

[0147] The polyarylene ethers according to the invention show a higher viscosity number compared to the linear polymers. In addition, the yield was improved. Also, the rate of incorporation of the ISOSO was high. In particular, the incorporation rate was higher in shorter condensation times. In addition, higher yields were obtained in shorter condensation times.

Examples MC1 to M5 Preparation of Membranes

Preparation of the Casting Solution as Well as the Membrane:

[0148] Into a three-neck flask equipped with a magnetic stirrer there was added 78 ml of NMP, 5 g of PVP (Luvitec® K40) and 17 g of the polyarylene ether. The mixture was heated under gentle stirring at 60° C. until a homogeneous clear viscous solution was obtained. The solution was 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.

[0149] 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.

[0150] 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:

[0151] 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.

TABLE-US-00004 TABLE 3 MC1* MC2* M3 M4 M5 C1 17 C2 17 3 17 4 17 PESU 17 PVP 5 5 5 5 5 NMP 78 78 78 78 78 PWP No Membrane 720 760 540 [l/m.sup.2*h*bar] membrane brittle MWCO [kD] 63 61 56 PWP 2 540 530 290 [l/m.sup.2*h*bar] *Comparative Examples Membranes prepared from the branched polyarylene ether comprising ISOSO showed a high permeability.

[0152] After filtration of the PEO-solution for the determination of the MWCO, the membrane was flushed twice with 500 ml portions of ultrapure water. Thereafter the PWP was measured again (PWP 2). The membranes prepared from the polyarylene ethers disclosed herein showed a higher flux-recovery.