Division of a polyarylene ether solution

Abstract

Process for producing polyarylene ether beads from a polyarylene ether solution, comprising the steps of i) dividing the polyarylene ether solution into droplets, ii) transferring the droplets into a precipitation bath to form polyarylene ether beads in the precipitation bath which (A) comprises at least one aprotic solvent (component (1)) and at least one protic solvent (component (2)), (B) has a temperature of 0° C. to T.sub.c, where the critical temperature T.sub.c in [° C.] can be determined by the numerical equation T.sub.c=(77−c)/0.58 in which c is the concentration of component (1) in the precipitation bath in [% by weight] and (C) has component (1) in concentrations of 5% by weight to c.sub.c, where the critical concentration c.sub.c in [% by weight] can be determined by the numerical equation c.sub.c=77−0.58*T in which T is the temperature in the precipitation bath in [° C.], where
the percentages by weight are each based on the sum of the percentages by weight of component (1) and of component (2) in the precipitation bath.

Claims

1. A process for producing polyarylene ether beads from a polyarylene ether solution, the process comprising: i) dividing the polyarylene ether solution into droplets; and ii) transferring the droplets into a precipitation bath to form polyarylene ether beads in the precipitation bath, wherein the precipitation bath (A) comprises at least one aprotic solvent (component (1)) and at least one protic solvent (component (2)); (B) has a temperature of 0° C. to T.sub.c, where the critical temperature T.sub.c in [° C.] can be determined by the numerical equation T.sub.c=(77−c)/0.58 in which c is the concentration of component (1) in the precipitation bath in [% by weight] and (C) has component (1) in a concentration of 12 to 70% by weight, where the percentage by weight is based on the sum of the percentages by weight of component (1) and of component (2) in the precipitation bath, wherein the precipitation bath comprises water or alcohol as component (2), wherein the polyarylene ether solution has a concentration of 5 to 50% by weight of polyarylene ether in the aprotic solvent, where the percentage by weight are based on the sum of the percentages by weight of the polyarylene ether and the aprotic solvent, wherein the polyarylene ether solution in the dividing has a temperature of 15 to 250° C., wherein the aprotic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, and wherein, in the polyarylene ether beads precipitated from the precipitation bath in (ii), the content of particles having a particle size of less than or equal to 1000 μm is less than 1.3% by weight.

2. The process according to claim 1, wherein the precipitation bath is agitated.

3. The process according to claim 1, wherein the polyarylene ether solution in the dividing has a temperature of 20 to 120° C.

4. The process according to claim 1, wherein the polyarylene ether solution after leaving a division apparatus covers a full distance from an exit point to a precipitation bath surface of 0.10 m to 1.20 m.

5. The process according to claim 1, wherein a division apparatus comprises a capillary or die plate.

6. The process according to claim 5, wherein the capillary or die plate has a diameter of 0.1 to 5.0 mm.

7. The process according to claim 1, wherein the polyarylene ether solution and the precipitation bath comprise the same aprotic solvent.

8. The process according to claim 1, wherein the precipitation bath comprises 12 to 50% by weight, of component (1), where the percentages by weight are each based on the sum of the percentages by weight of component (1) and component (2) in the precipitation bath.

9. The process according to claim 1, further comprising stirring the precipitation bath when transferring the droplets into the precipitation bath.

10. The process according to claim 1, wherein the polyarylene ether beads are individual beads which are not agglomerated.

11. The process of claim 1, wherein, in the polyarylene ether beads precipitated from the precipitation bath in (ii), the content of particles having a particle size of less than or equal to 1000 μm is 0.93% by weight or less.

12. The process according to claim 1, wherein the polyarylene ether beads are individual beads which are not agglomerated.

13. A process for producing polyarylene ether beads of claim 1 from a polyarylene ether solution, the process comprising: i) dividing the polyarylene ether solution into droplets; and ii) transferring the droplets into a precipitation bath to form polyarylene ether beads in the precipitation bath, wherein the precipitation bath (A) comprises at least one aprotic solvent (component (1)) and at least one protic solvent (component (2)); (B) has a temperature of 0° C. to T.sub.c, where the critical temperature T.sub.c in [° C.] can be determined by the numerical equation T.sub.c=(77−c)/0.58 in which c is the concentration of component (1) in the precipitation bath in [% by weight] and (C) has component (1) in a concentration of 12 to 70% by weight, where the percentage by weight is based on the sum of the percentages by weight of component (1) and of component (2) in the precipitation bath, wherein the precipitation bath comprises water or alcohol as component (2), wherein the polyarylene ether solution has a concentration of 5 to 50% by weight of polyarylene ether in the aprotic solvent, where the percentage by weight are based on the sum of the percentages by weight of the polyarylene ether and the aprotic solvent, wherein the polyarylene ether solution in the dividing has a temperature of 15 to 250° C., wherein the aprotic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, and wherein the polyarylene ether comprises at least one repeat structural unit selected from the group consisting of: ##STR00006## ##STR00007##

14. The process of claim 13, wherein the polyarylene ether comprises at least one repeat structural unit selected from the group consisting of: ##STR00008##

15. The process of claim 1, wherein the aprotic solvent is N-methyl-2-pyrrolidone.

Description

EXAMPLES

Examples 1 to 171: Variation of Precipitation Bath Temperature and Precipitation Bath Composition

(1) Experiments 1 to 171 were conducted successively, each with two illustrative polyarylene ether solutions, with optimization of the precipitation behavior.

(2) Solution 1: A solution comprising a polyarylene ether having elements of the structure I (formula II) was dissolved in NMP and the respective concentration was set (see tables, polyarylene ether solution). The polyarylene ether used, having elements of the structure I, had a viscosity number of 56 ml/g. The viscosity number determination was conducted to ISO1628 from a 0.01 g/ml solution in phenol/1,2-dichlorobenzene (1:1) at 25° C.

(3) ##STR00004##

(4) Solution 2: A solution comprising a polyarylene ether having elements of the structure I (formula II) was dissolved in NEP and the respective concentration was set (see tables, polyarylene ether solution). The polyarylene ether used, having elements of the structure I, had a viscosity number of 56 ml/g. The viscosity number determination was conducted to ISO1628 from a 0.01 g/ml solution in phenol/1,2-dichlorobenzene (1:1) at 25° C.

(5) Solution 3: A solution comprising a polyarylene ether having elements of the structure II (formula III) was dissolved in NMP and the respective concentration was set (see tables, polyarylene ether solution). The polyarylene ether used, having elements of the structure II, had a viscosity number of 63 ml/g. The viscosity number determination was conducted to ISO1628 from a 0.01 g/ml solution in phenol/1,2-dichlorobenzene (1:1) at 25° C.

(6) ##STR00005##

(7) Solution 4: A solution comprising a polyarylene ether having elements of the structure 11 (formula III) was dissolved in NEP and the respective concentration was set (see tables, polyarylene ether solution). The polyarylene ether used, having elements of the structure II, had a viscosity number of 63 ml/g.

(8) The viscosity number determination was conducted to ISO1628 from a 0.01 g/ml solution in phenol/1,2-dichlorobenzene (1:1) at 25° C.

(9) Solution 1 or the solutions 2, 3 or 4, each of set concentration, was run from a reservoir vessel at a constant delivery rate of 600 g/h through a capillary for division to form droplets. The experiments were conducted with a capillary as the die. The capillary diameter and the fall distance from exit from the capillary and precipitation bath surface were varied, as specified in the tables below.

(10) After the division, the droplet of the respective polymer solution fell into a precipitation bath. The precipitation bath composition (NMP as component (1).1 or NEP as component (1).2 and water as component (2).1) was varied as specified in the tables. The temperature of the precipitation bath was kept constant during an experiment. The beads formed in the process were separated off using a screen and examined further.

(11) The experiment was conducted at different precipitation bath temperatures.

(12) In the experiments with solutions 1 and 3, the NMP content in the precipitation bath was controlled with the aid of a refractometer at 25° C. The instrument used was an Abbe refractometer from Leo Kübler GmbH (model: Atago). A drop of the water/NMP mixture was taken from the precipitation medium to measure the refractive index. Using a calibration curve of NMP/water composition versus refractive index, it was possible to control or measure the precipitation bath composition.

(13) The same method for determining the NEP content was used in the experiments with solutions 2 and 4. For this purpose, a calibration curve of NEP/water composition versus refractive index was produced.

(14) NMP Solvent, Solution 1

(15) Variation of the NMP content of the precipitation bath at precipitation bath temperature 10° C.:

(16) TABLE-US-00001 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 1 1 14.2 25 0.8 20 10 20 Individual beads 2 1 14.2 25 0.8 20 10 30 Individual beads 3 1 14.2 25 0.8 20 10 40 Individual beads 4 1 14.2 25 0.8 20 10 50 Individual beads 5 1 14.2 25 0.8 20 10 65 Individual beads 6 1 14.2 25 0.8 20 10 72 Beads which agglomerate in the precipitation bath

(17) Variation of the NMP content of the precipitation bath at precipitation bath temperature 20° C.:

(18) TABLE-US-00002 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 7 1 14.2 25 0.8 20 20 20 Individual beads 8 1 14.2 25 0.8 20 20 30 Individual beads 9 1 14.2 25 0.8 20 20 40 Individual beads 10 1 14.2 25 0.8 20 20 50 Individual beads 11 1 14.2 25 0.8 20 20 60 Individual beads 12 1 14.2 25 0.8 20 20 66 Beads which agglomerate in the precipitation bath

(19) Variation of the NMP content of the precipitation bath at precipitation bath temperature 30° C.:

(20) TABLE-US-00003 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 13 1 14.2 25 0.8 20 30 20 Individual beads 14 1 14.2 25 0.8 20 30 30 Individual beads 15 1 14.2 25 0.8 20 30 40 Individual beads 16 1 14.2 25 0.8 20 30 50 Individual beads 17 1 14.2 25 0.8 20 30 55 Individual beads 18 1 14.2 25 0.8 20 30 60 Beads which agglomerate in the precipitation bath

(21) Variation of the NMP content of the precipitation bath at precipitation bath temperature 40° C.:

(22) TABLE-US-00004 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 19 1 14.2 25 0.8 20 40 20 Individual beads 20 1 14.2 25 0.8 20 40 30 Individual beads 21 1 14.2 25 0.8 20 40 40 Individual beads 22 1 14.2 25 0.8 20 40 50 Individual beads 23 1 14.2 25 0.8 20 40 55 Beads which agglomerate in the precipitation bath

(23) Variation of the NMP content of the precipitation bath at precipitation bath temperature 50° C.:

(24) TABLE-US-00005 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 24 1 14.2 25 0.8 20 50 20 Individual beads 25 1 14.2 25 0.8 20 50 30 Individual beads 26 1 14.2 25 0.8 20 50 40 Individual beads 27 1 14.2 25 0.8 20 50 45 Individual beads 28 1 14.2 25 0.8 20 50 49 Beads which agglomerate in the precipitation bath

(25) Variation of the NMP content of the precipitation bath at precipitation bath temperature 60° C.:

(26) TABLE-US-00006 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 29 1 14.2 25 0.8 20 60 20 Individual beads 30 1 14.2 25 0.8 20 60 30 Individual beads 31 1 14.2 25 0.8 20 60 35 Individual beads 32 1 14.2 25 0.8 20 60 40 Individual beads 33 1 14.2 25 0.8 20 60 43 Beads which agglomerate in the precipitation bath

(27) Variation of the NMP content of the precipitation bath at precipitation bath temperature 70° C.:

(28) TABLE-US-00007 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 34 1 14.2 25 0.8 20 70 20 Individual beads 35 1 14.2 25 0.8 20 70 30 Individual beads 36 1 14.2 25 0.8 20 70 33 Individual beads 37 1 14.2 25 0.8 20 70 38 Beads which agglomerate in the precipitation bath

(29) Variation of the NMP content of the precipitation bath at precipitation bath temperature 85° C.:

(30) TABLE-US-00008 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 38 1 25 25 1.5 70 85 20 Individual beads 39 1 25 25 1.5 70 85 25 Individual beads 40 1 25 25 1.5 70 85 30 Beads which agglomerate in the precipitation bath

(31) The NMP content in the precipitation bath was increased from 20% by weight until the beads present in the precipitation bath agglomerated. Agglomeration of the beads is disadvantageous since such beads cannot be processed any further.

(32) NEP Solvent, Solution 2

(33) Variation of the NEP content of the precipitation bath at precipitation bath temperature 10° C.:

(34) TABLE-US-00009 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 41 2 16 25 0.8 40 10 20 Individual beads 42 2 16 25 0.8 40 10 30 Individual beads 43 2 16 25 0.8 40 10 40 Individual beads 44 2 16 25 0.8 40 10 50 Individual beads 45 2 16 25 0.8 40 10 65 Individual beads 46 2 16 25 0.8 40 10 72 Beads which agglomerate in the precipitation bath

(35) Variation of the NEP content of the precipitation bath at precipitation bath temperature 20° C.:

(36) TABLE-US-00010 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 47 2 16 25 0.8 40 20 20 Individual beads 48 2 16 25 0.8 40 20 30 Individual beads 49 2 16 25 0.8 40 20 40 Individual beads 50 2 16 25 0.8 40 20 50 Individual beads 51 2 16 25 0.8 40 20 60 Individual beads 52 2 16 25 0.8 40 20 66 Beads which agglomerate in the precipitation bath

(37) Variation of the NEP content of the precipitation bath at precipitation bath temperature 35° C.:

(38) TABLE-US-00011 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 53 2 16 25 0.8 40 35 20 Individual beads 54 2 16 25 0.8 40 35 30 Individual beads 55 2 16 25 0.8 40 35 40 Individual beads 56 2 16 25 0.8 40 35 50 Individual beads 57 2 16 25 0.8 40 35 55 Individual beads 58 2 16 25 0.8 40 35 58 Beads which agglomerate in the precipitation bath

(39) Variation of the NEP content of the precipitation bath at precipitation bath temperature 50° C.:

(40) TABLE-US-00012 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 59 2 16 25 0.8 40 40 20 Individual beads 60 2 16 25 0.8 40 40 30 Individual beads 61 2 16 25 0.8 40 40 40 Individual beads 62 2 16 25 0.8 40 40 45 Individual beads 63 2 16 25 0.8 40 40 50 Beads which agglomerate in the precipitation bath

(41) Variation of the NEP content of the precipitation bath at precipitation bath temperature 60° C.:

(42) TABLE-US-00013 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 64 2 16 25 0.8 40 60 20 Individual beads 65 2 16 25 0.8 40 60 30 Individual beads 66 2 16 25 0.8 40 60 35 Individual beads 67 2 16 25 0.8 40 60 40 Individual beads 68 2 16 25 0.8 40 60 43 Beads which agglomerate in the precipitation bath

(43) Variation of the NEP content of the precipitation bath at precipitation bath temperature 70° C.:

(44) TABLE-US-00014 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 69 2 16 25 0.8 40 70 20 Individual beads 70 2 16 25 0.8 40 70 30 Individual beads 71 2 16 25 0.8 40 70 33 Individual beads 72 2 16 25 0.8 40 70 38 Beads which agglomerate in the precipitation bath

(45) The NEP content in the precipitation bath was increased from 20% by weight until the beads present in the precipitation bath agglomerated. Agglomeration of the beads is disadvantageous since such beads cannot be processed any further.

(46) Variation of the precipitation bath temperature at NMP content 30% in the precipitation bath:

(47) TABLE-US-00015 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 73 1 20 25 1 20 60 30 Individual beads 74 1 20 25 1 20 70 30 Individual beads 75 1 20 25 1 20 80 30 Individual beads 76 1 20 25 1 20 86 30 Beads which agglomerate in the precipitation bath 77 1 25 25 1.5 70 60 30 Individual beads 78 1 25 25 1.5 70 70 30 Individual beads 79 1 25 25 1.5 70 80 30 Individual beads 80 1 25 25 1.5 70 86 30 Beads which agglomerate in the precipitation bath 81 1 25 90 1.5 70 60 30 Individual beads 82 1 25 90 1.5 70 70 30 Individual beads 83 1 25 90 1.5 70 80 30 Individual beads 84 1 25 90 1.5 70 86 30 Beads which agglomerate in the precipitation bath
NMP Solvent, Solution 3

(48) Variation of the NMP content of the precipitation bath at precipitation bath temperature 10° C.:

(49) TABLE-US-00016 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 85 3 15 25 0.8 30 10 20 Individual beads 86 3 15 25 0.8 30 10 30 Individual beads 87 3 15 25 0.8 30 10 40 Individual beads 88 3 15 25 0.8 30 10 50 Individual beads 89 3 15 25 0.8 30 10 65 Individual beads 90 3 15 25 0.8 30 10 72 Beads which agglomerate in the precipitation bath

(50) Variation of the NMP content of the precipitation bath at precipitation bath temperature 20° C.:

(51) TABLE-US-00017 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 91 3 15 25 0.8 30 20 20 Individual beads 92 3 15 25 0.8 30 20 30 Individual beads 93 3 15 25 0.8 30 20 40 Individual beads 94 3 15 25 0.8 30 20 50 Individual beads 95 3 15 25 0.8 30 20 60 Individual beads 96 3 15 25 0.8 30 20 66 Beads which agglomerate in the precipitation bath

(52) Variation of the NMP content of the precipitation bath at precipitation bath temperature 30° C.:

(53) TABLE-US-00018 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 97 3 15 25 0.8 30 30 20 Individual beads 98 3 15 25 0.8 30 30 30 Individual beads 99 3 15 25 0.8 30 30 40 Individual beads 100 3 15 25 0.8 30 30 50 Individual beads 101 3 15 25 0.8 30 30 55 Individual beads 102 3 15 25 0.8 30 30 60 Beads which agglomerate in the precipitation bath

(54) Variation of the NMP content of the precipitation bath at precipitation bath temperature 40° C.:

(55) TABLE-US-00019 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 103 3 15 25 0.8 30 40 20 Individual beads 104 3 15 25 0.8 30 40 30 Individual beads 105 3 15 25 0.8 30 40 40 Individual beads 106 3 15 25 0.8 30 40 50 Individual beads 107 3 15 25 0.8 30 40 55 Beads which agglomerate in the precipitation bath

(56) Variation of the NMP content of the precipitation bath at precipitation bath temperature 50° C.:

(57) TABLE-US-00020 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 108 3 15 25 0.8 30 50 20 Individual beads 109 3 15 25 0.8 30 50 30 Individual beads 110 3 15 25 0.8 30 50 40 Individual beads 111 3 15 25 0.8 30 50 45 Individual beads 112 3 15 25 0.8 30 50 49 Beads which agglomerate in the precipitation bath

(58) Variation of the NMP content of the precipitation bath at precipitation bath temperature 60° C.:

(59) TABLE-US-00021 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 113 3 15 25 0.8 30 60 20 Individual beads 114 3 15 25 0.8 30 60 30 Individual beads 115 3 15 25 0.8 30 60 35 Individual beads 116 3 15 25 0.8 30 60 40 Individual beads 117 3 15 25 0.8 30 60 43 Beads which agglomerate in the precipitation bath

(60) Variation of the NMP content of the precipitation bath at precipitation bath temperature 70° C.:

(61) TABLE-US-00022 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 118 3 15 25 0.8 30 70 20 Individual beads 119 3 15 25 0.8 30 70 30 Individual beads 120 3 15 25 0.8 30 70 33 Individual beads 121 3 15 25 0.8 30 70 38 Beads which agglomerate in the precipitation bath

(62) The NMP content in the precipitation bath was increased from 20% by weight until the beads present in the precipitation bath agglomerated. Agglomeration of the beads is disadvantageous since such beads cannot be processed any further.

(63) NEP Solvent, Solution 4

(64) Variation of the NEP content of the precipitation bath at precipitation bath temperature 10° C.:

(65) TABLE-US-00023 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 122 4 15 25 0.8 20 10 20 Individual beads 123 4 15 25 0.8 20 10 30 Individual beads 124 4 15 25 0.8 20 10 40 Individual beads 125 4 15 25 0.8 20 10 50 Individual beads 126 4 15 25 0.8 20 10 65 Individual beads 127 4 15 25 0.8 20 10 72 Beads which agglomerate in the precipitation bath

(66) Variation of the NEP content of the precipitation bath at precipitation bath temperature 20° C.:

(67) TABLE-US-00024 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 128 4 15 25 0.8 20 20 20 Individual beads 129 4 15 25 0.8 20 20 30 Individual beads 130 4 15 25 0.8 20 20 40 Individual beads 131 4 15 25 0.8 20 20 50 Individual beads 132 4 15 25 0.8 20 20 60 Individual beads 133 4 15 25 0.8 20 20 66 Beads which agglomerate in the precipitation bath

(68) Variation of the NEP content of the precipitation bath at precipitation bath temperature 30° C.:

(69) TABLE-US-00025 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 134 4 15 25 0.8 20 30 20 Individual beads 135 4 15 25 0.8 20 30 30 Individual beads 136 4 15 25 0.8 20 30 40 Individual beads 137 4 15 25 0.8 20 30 50 Individual beads 138 4 15 25 0.8 20 30 55 Individual beads 139 4 15 25 0.8 20 30 60 Beads which agglomerate in the precipitation bath

(70) Variation of the NEP content of the precipitation bath at precipitation bath temperature 40° C.:

(71) TABLE-US-00026 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 140 4 15 25 0.8 20 40 20 Individual beads 141 4 15 25 0.8 20 40 30 Individual beads 142 4 15 25 0.8 20 40 40 Individual beads 143 4 15 25 0.8 20 40 50 Individual beads 144 4 15 25 0.8 20 40 55 Beads which agglomerate in the precipitation bath

(72) Variation of the NEP content of the precipitation bath at precipitation bath temperature 50° C.:

(73) TABLE-US-00027 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 145 4 15 25 0.8 20 50 20 Individual beads 146 4 15 25 0.8 20 50 30 Individual beads 147 4 15 25 0.8 20 50 40 Individual beads 148 4 15 25 0.8 20 50 45 Individual beads 149 4 15 25 0.8 20 50 49 Beads which agglomerate in the precipitation bath

(74) Variation of the NEP content of the precipitation bath at precipitation bath temperature 60° C.:

(75) TABLE-US-00028 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 150 4 15 25 0.8 20 60 20 Individual beads 151 4 15 25 0.8 20 60 30 Individual beads 152 4 15 25 0.8 20 60 35 Individual beads 153 4 15 25 0.8 20 60 40 Individual beads 154 4 15 25 0.8 20 60 43 Beads which agglomerate in the precipitation bath

(76) Variation of the NEP content of the precipitation bath at precipitation bath temperature 70° C.:

(77) TABLE-US-00029 Precipitation bath Polyarylene ether solution Precipitation NEP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 155 4 15 25 0.8 20 70 20 Individual beads 156 4 15 25 0.8 20 70 30 Individual beads 157 4 15 25 0.8 20 70 33 Individual beads 158 4 15 25 0.8 20 70 38 Beads which agglomerate in the precipitation bath

(78) The NEP content in the precipitation bath was increased from 20% by weight until the beads present in the precipitation bath agglomerated. Agglomeration of the beads is disadvantageous since such beads cannot be processed any further.

(79) Variation of the precipitation bath temperature at NMP content 30% in the precipitation bath:

(80) TABLE-US-00030 Precipitation bath Polyarylene ether solution Precipitation NMP Solution Conc. T Die diameter height T content Precipitation Ex. number [% by wt.] [° C.] [mm] [cm] [° C.] [% by wt.] characteristics 160 3 20 25 1 20 60 30 Individual beads 161 3 20 25 1 20 70 30 Individual beads 162 3 20 25 1 20 80 30 Individual beads 163 3 20 25 1 20 85 30 Beads which agglomerate in the precipitation bath 164 3 25 25 1 60 60 30 Individual beads 165 3 25 25 1 60 70 30 Individual beads 166 3 25 25 1 60 80 30 Individual beads 167 3 25 25 1 60 85 30 Beads which agglomerate in the precipitation bath 168 3 25 90 1 60 60 30 Individual beads 169 3 25 90 1 60 70 30 Individual beads 170 3 25 90 1 60 80 30 Individual beads 171 3 25 90 1 60 85 30 Beads which agglomerate in the precipitation bath

(81) Examples 172 to 175 show the influence of the NMP concentration in the precipitation bath on the formation of fines. “Fines” are understood here to mean polyarylene ether beads having a particle size of ≦1000 μm.

(82) For this purpose, a solution 5 of polyarylene ether in NMP was prepared. The polyarylene ether used was Ultrason® E2020 from BASF SE. The concentration of the polyarylene ether was 18.0% by weight.

(83) The polyarylene ether was precipitated by means of dropletization and then extracted.

(84) For the dropletization, solution 5 was introduced into the reservoir vessel and adjusted to the desired temperature. By means of a gear pump, solution 5 was dropletized through a capillary. The precipitation was effected in a precipitation bath with an overflow to an agitated screen which removed the beads. The precipitation bath solution was collected in a buffer vessel and then sent back to the precipitation bath.

(85) The concentration of NMP in the precipitation bath was monitored by means of refractive index and balanced by addition of demineralized water. After dropletization had ended, the beads/lenses were filtered off with suction, washed with demineralized water and then extracted.

(86) The conditions during the dropletization are specified in the following table.

(87) TABLE-US-00031 Conc. in Conc. solv. in the Precipitation Temp. of solution 5 Fall solution 5 precipitation bath bath temp. on dropletization height Exp. Solvent [% by wt.] [%] [° C.] [° C.] [cm] 172 NMP 18.0 40 40 40 30 173 NMP 18.0 <1 40 40 30

(88) The conditions in the extraction with water were as follows:

(89) Temp. in the extraction: 95° C.

(90) Extractant throughput: 2000 ml water/h

(91) Extractant temp.: 90-95° C.

(92) Extraction period: 24 h

(93) The particle size distribution was determined as follows:

(94) The extracted moist beads/lenses were dried in a drying cabinet at 60° C. and then the distribution was determined by means of manual screening in a screening tower. The results are reported in the table which follows.

(95) TABLE-US-00032 Particle size [μm] 172 173 3150 100.0 99.80 2800 99.78 99.01 2500 98.49 97.43 2000 54.96 30.56 1600 8.62 5.84 1250 3.45 2.67 1000 1.08 1.68  650 0.22 0.69 Sum ≦1000 = 1.3 2.37 fines

(96) Examples 174 and 175 were conducted analogously to examples 172 and 173. The fall height and the temperature were altered; the concentration of the precipitation bath was varied. The results are reported in the table which follows.

(97) TABLE-US-00033 Precipitation bath PES soln. Fines Conc. NMP Temp. SC Temp. Fall height fraction <1 Exp. [%] [° C.] [%] [° C.] [cm] mm [%] 174 20 35 23 65 90 0.37 175 1 35 23 65 90 0.93

(98) Examples 172 to 175 show that, within the inventive concentration range of aprotic solvent in the precipitation bath, polyarylene ether beads having a distinctly smaller fines fraction are obtained.