Crystal composition (CC) comprising 4,4#-dichlorodiphenylsulfoxide crystals (C)

Abstract

The invention relates to a crystal (C) consisting of at least 95% by weight of 4,4′-dichlorodiphenylsulfoxide, 0 to 2% by weight of impurities and 0 to 3% by weight of an organic solvent (os). Moreover, the present invention relates to a crystal composition (CC) comprising crystals (C) and a process for the production of the crystal composition (CC) and the crystal (C).

Claims

1. A crystal composition (CC), comprising crystals (C), wherein the crystals (C) consist of (a) at least 95% by weight of 4,4′-dichlorodiphenylsulfoxide, (b) 0 to 2% by weight of impurities, and (c) 0 to 3% by weight of an organic solvent (os), based on a total weight of the crystals (C) comprised in the crystal composition (CC), wherein the crystal composition (CC) has a d10,.sub.3-value in a range of 100 to 400 μm, a d50,.sub.3-value in a range of 300 to 800 μm and a d90,.sub.3-value in a range of 700 to 1500 μm, wherein the d10,.sub.3-value is lower than the d50,.sub.3-value and the d50,.sub.3-value is lower than the d90,.sub.3-value.

2. The crystal composition (CC) of claim 1, wherein the crystal composition (CC) comprises at least 95% by weight of the crystals (C), based on a total weight of the crystal composition (CC).

3. The crystal composition (CC) of claim 1, wherein the crystal composition (CC) has a bulk density in a range of 600 to 950 kg/m.sup.3.

4. The crystal composition (CC) of claim 1, wherein an average aspect ratio of the crystals (C) is in a range of 0.2 to 1.

5. The crystal composition (CC) of claim 1, wherein an average sphericity of the crystals (C) is in a range of 0.75 to 0.85.

6. The crystal composition (CC) of claim 1, wherein a Hausner ratio is in a range of 1.05 to 1.27.

7. The crystal composition (CC) of claim 1, wherein a unit cell of the crystals (C) is monoclinic, space group C 2/m, cell lengths a=16.05 ű0.05 Å, b=9.82 ű0.05 Å, c=7.21 ű0.05 Å, cell angles alpha 90°±0.1°, beta 95.7°±0.1°, gamma 90°±0.1°, and a cell volume 1131.5 Å.sup.3±1 Å.sup.3.

8. A crystal (C) consisting of (a) at least 95% by weight 4,4′-dichlorodiphenylsulfoxide, (b) 0 to 2% by weight of impurities, and (c) 0 to 3% by weight of an organic solvent (os), based in each case on a total weight of the crystal (C), wherein an outer surface of the crystal (C) comprises i) a six-sided base surface (bsu), ii) a six-sided top surface (tsu), and iii) six side surfaces (ssu1 to ssu6), joining the corresponding sides of the six-sided base surface (bsu) and the six-sided top surface (tsu).

9. The crystal (C) of claim 8, wherein the six-sided base surface (bsu), the six-sided top surface (tsu) and the six side surfaces (ssu1 to ssu6) account for at least 90% of the outer surface of the crystal (C).

10. The crystal (C) of claim 8, wherein a diameter (db) of the six-sided base surface (bsu) and a diameter (dt) of the six-sided top surface (tsu) are each independently in a range of 50 to 1500 μm.

11. The crystal (C) of claim 8, wherein a length (l1) of the first side surface (ssu1), a length (l2) of the second side surface (ssu2), a length (l3) of the third side surface (ssu3), a length (l4) of the fourth side surface (ssu4), a length (l5) of the fifth side surface (ssu5) and a length (l6) of the sixth side surface (ssu6) are each independently in a range of 100 to 3000 μm.

12. The crystal (C) of claim 8, wherein a ratio of an average of a diameter (db) of the six-sided base surface (bsu) and a diameter (dt) of the six-sided top surface (tsu) to an average of a length (l1) of the first side surface (ssu1), a length (l2) of the second side surface (ssu2), a length (l3) of the third side surface (ssu3), a length (l4) of the fourth side surface (ssu4), a length (l5) of the fifth side surface (ssu5) and a length (l6) of the sixth side surface (ssu6) is in a range of 0.2 to 1.

13. The crystal (C) of claim 8, wherein the impurities (b) comprise at least 90% by weight of one or more compounds selected from the group consisting of 2,4′-dichlorodiphenylsulfoxide, 3,4′-dichlorodiphenylsulfoxide, 2,2′-dichlorodiphenylsulfoxide, 4,4′-dichlorodiphenylsulfide, and one or more aluminum compounds based on a total weight of the impurities (b) comprised in the crystal (C).

14. The crystal composition (CC) of claim 1, obtained by a process comprising: I) cooling a first liquid mixture comprising 4,4′-dichlorodiphenylsulfoxide dissolved in an organic solvent (os) to obtain a suspension comprising crystallized 4,4′-dichlorodiphenylsulfoxide and the organic solvent (os), II) filtering the suspension obtained in I) to obtain a filtrate comprising 4,4′-dichlorodiphenylsulfoxide dissolved in the organic solvent (os), wherein the filtrate has a lower concentration of 4,4′-dichlorodiphenylsulfoxide compared to the first liquid mixture, and a filter residue comprising the crystallized 4,4′-dichlorodiphenylsulfoxide, III) concentrating the filtrate obtained in II) to obtain a second liquid mixture, wherein the second liquid mixture has a higher concentration of 4,4′-dichlorodiphenylsulfoxide compared to the filtrate, IV) recycling at least a part of the second liquid mixture obtained in III) into I), and V) drying the filter residue obtained in II) to obtain the crystal composition (CC).

15. The crystal (C) of claim 8, obtained by a process comprising: I) cooling a liquid mixture comprising 4,4′-dichlorodiphenylsulfoxide dissolved in an organic solvent (os) to obtain a suspension comprising crystallized 4,4′-dichlorodiphenylsulfoxide and the organic solvent (os), II) filtering the suspension obtained in I) to obtain a filtrate comprising 4,4′-dichlorodiphenylsulfoxide dissolved in the organic solvent (os), wherein the filtrate has a lower concentration of 4,4′-dichlorodiphenylsulfoxide compared to the liquid mixture, and a filter residue comprising the crystallized 4,4′-dichlorodiphenylsulfoxide, V) drying the filter residue obtained in II) to obtain a crystal composition (CC), and VI) separating a crystal (C) from the crystal composition (CC) obtained in V).

16. A method of producing a monomer, polymer, or pharmaceutical, the method comprising reacting a crystal composition (CC) as an intermediate, wherein the crystal composition (CC) comprises crystals (C), wherein the crystals (C) consist of (a) at least 95% by weight of 4,4′-dichlorodiphenylsulfoxide, (b) 0 to 2% by weight of impurities, and (c) 0 to 3% by weight of an organic solvent (os), based on a total weight of the crystals (C) comprised in the crystal composition (CC), wherein the crystal composition (CC) has a d10,.sub.3-value in a range of 100 to 400 μm, a d50,.sub.3-value in a range of 300 to 800 μm and a d90,.sub.3-value in a range of 700 to 1500 μm, wherein the d10,.sub.3-value is lower than the d50,.sub.3-value and the d50,.sub.3-value is lower than the d90,.sub.3-value.

Description

EXAMPLES

(1) Production of the Crystal Composition (CC)/the Crystal (C) According to the Invention

(2) For the production of 4,4′-dichlorodiphenylsulfoxide (DCDPSO) 5.5 mol aluminum chloride and 40 mol monochlorobenzene (MCB) were fed into a stirred tank reactor as a first reactor. Subsequently 5 mol thionyl chloride were added into the first reactor within 160 minutes. The reaction in the first reactor was carried out at a temperature of 10° C. The hydrogen chloride produced during the reaction was withdrawn from the first reactor. After finishing the addition of thionyl chloride the reaction mixture in the first reactor was heated to 60° C.

(3) After completion of the reaction in the first reactor, the resulting reaction mixture was fed into a stirred tank reactor as a second reactor containing 3400 g aqueous hydrochloric acid with a concentration of 11% by weight. The second reactor was heated to a temperature of 90° C. with stirring. After 30 minutes the stirring was stopped and the mixture contained in the second reactor separated into an aqueous phase and in organic phase. The aqueous phase was withdrawn.

(4) The organic phase was washed with 3000 g water while stirring at 90° C. After washing, the stirring was stopped and the mixture separated into an aqueous phase and in organic phase. The aqueous phase was removed. The organic phase was subjected to a distillation.

(5) Monchlorobenzene was distilled from said organic phase until saturation is reached. The distillation was carried out at a temperature of 88 to 90° C. at a pressure of 200 mbar (abs). The saturation was monitored via a turbidity probe.

(6) Subsequently an evaporation cooling crystallization was performed with the saturated organic phase containing monochlorobenzene and 4,4′-dichlorodiphenylsulfoxide obtained in the above described distillation (equals cooling step I) of the present invention) until the temperature reached 20° C. Therefore, the organic phase was refluxed due to pressure reduction and simultaneously cooled by the condensed liquid. The pressure at the end of the evaporation cooling process is normally about 20 mbar (abs). After the evaporation cooling crystallization a suspension was obtained comprising a crystallized 4,4′-dichlorodiphenylsulfoxide and monochlorobenzene.

(7) According to step II) of the present invention the suspension obtained in step I) was filtered to obtain a filtrate comprising 4,4′-dichlorodiphenylsulfoxide dissolved in monochlorobenzene and a filter residue comprising the crystallized 4,4′-dichlorodiphenylsulfoxide. The filter residue was washed with monochlorobenzene and subsequently dried at 100° C. and 100 mbar (abs) in order to obtain the crystal composition (CC) (equals step V) of the present invention).

(8) According to step III) the washing filtrate and the filtrate obtained in step II) were subjected to a distillation. In the distillation monochlorobenzene was removed until the amount of combined filtrate and washing filtrate was reduced to 25% by weight. The distillation was operated at 90° C. sump temperature and 200 mbar (abs). The distilled monochlorobenzene was reused in the next batch as starting material. 80% by weight of the obtained bottom product (equals second liquid mixture according to step III) of the present invention) were recycled into the crystallization step of the next batch (equals the cooling step I) according to the present invention).

(9) The crystal composition (CC) was obtained in a steady state yield of 1232 g per batch which corresponds to a yield of 91.3%.

(10) 4,4′-dichlorodiphenylsulfoxide obtained from commercial suppliers: abcr-DCDPSO: 4,4′-dichlorodiphenylsulfoxide obtained from abcr GmbH Alfa-DCDPSO: 4,4′-dichlorodiphenylsulfoxide obtained from Alfa-Aesar TCI-DCDPSO: 4,4′-dichlorodiphenylsulfoxide obtained from TCI GmbH Recryst-DCDPSO: 4,4′-dichlorodiphenylsulfoxide recrystallized from diethylether Recryst-DCDPSO; CHCl.sub.3: 4,4′-dichlorodiphenylsulfoxide recrystallized from chloroform Recryst-DCDPSO; EA: 4,4′-dichlorodiphenylsulfoxide recrystallized from ethyl acetate
Analytical Methods

(11) The d10,.sub.3-values, the d50,.sub.3-values and the d90,.sub.3-values are determined as described above using a Camsizer®XT with a measuring method x.sub.area.

(12) GC analysis was performed to determine any organic impurity, solvent and the purity of the 4,4′-dichlorodiphenylsulfoxide. Samples were diluted in dimethylformamide (DM F) and the internal standard tridecane was added to quantify the components based on calibration curves. GC analysis was performed using a RTx5 Amine column (0.25 μm) from Restek® using the following temperature ramp: holding 50° C. for 2 minutes, heating 15° C. per minute until 250° C. is reached, holding 250° C. for 15 minutes.

(13) APHA numbers were measured (as described above) on a Hach Lange LICO 500 instrument; 2.5 g 4,4′-dichlorodiphenylsulfoxide were dissolved in 20 mL N-methyl-2-pyrrolidone (NMP) and measured against pure NMP.

(14) Determination of the aluminum content was done by generating a saturated solution of 4,4′-dichlorodiphenylsulfoxide in dimethylformamide to generate a homogeneous solution. Subsequently, a sample of said saturated solution was taken and the weight was determined (100 to 200 mg+/−0.1 mg). Afterwards, the following decomposition process was conducted. 8 ml of concentrated sulfuric acid (96% w/w) were added to the sample and heated to 320° C. Subsequently, 7 ml of a mixed acid (H.sub.2SO.sub.4 96% w/w; HClO.sub.4 70% w/w; HNO.sub.3 65% w/w in a volume ratio 2:1:1) were added and the sample as then heated to 160° C. Thereafter, the excess acid was evaporated. Subsequently 12 ml of hydrochloric acid (HCl 36% w/w) were added and the mixture was heated to reflux to obtain a solution. The exact volume of said solution was determined by back weighting and correction with the density. Thereafter, the aluminum content of the solution was measured by inductively coupled optical plasma emission spectroscopy. (Instrument IPC-OES Agilent 5100; wave length Al 394, 401 nm; internal standard SC 361.383 nm)

(15) Bulk density and tapered density were determined as described above.

(16) The flowability (ff.sub.c) was determined on a Ring Shear Tester RST-XS according to Jenike as described in Dr.-Ing. Dietmar Schulze “The automatic Ring Shear Tester RST-01.pc” and ASTM-D 6773 at an initial shear stress of 3 kPa.

(17) According to Jenike the flowability is classified according the following table:

(18) TABLE-US-00003 ff.sub.c Flowability <1 Not flowing 1 < to <2 Very poor 2 < to <4 Poor 4 < to <10 Good 10 < Excellent

(19) The melting point was determined by DSC (Differential Scanning calorimetry) on a Mettler Toledo DSC3 using a heating rate of 2.5 K/min (30 to 410° C.).

(20) The results are shown in the below table.

(21) TABLE-US-00004 Tapered bulk density Purity MCB Al Particle Bulk (1250 Flow- Melting [wt.- Impurities [wt.- content size APHA density lifts) Hausner ability point Color %] [wt.- %] %] [ppm] [μm] number [kg/m.sup.3] [kg/m.sup.3] ratio [ttc] [° C.] abcr- yellow 99.1 4,4′-dichlorodi- 0.17 n.d. 960 d10.sub.,3 = 17 >4000 n.d. n.d. n.d. 6.5 ± 141.4- DCDPSO powder phenylsulfide d50.sub.,3 = 31 0.4 142.5 2,4′-dichlorodi- 0.17 d90.sub.,3 = 62 phenylsulfoxide TCI- white 99.1 2,4′-dichlorodi- 0.20 n.d. <60 d10.sub.,3 = 53 472 n.d. n.d. n.d. 5.8 ± 141.9- DCDPSO crystals phenylsulfoxide d50.sub.,3 = 491 0.6 143.6 d90.sub.,3 = 1063 Alfa- white 97.4 4,4′-dichlorodi- 0.26 1.12 <60 d10.sub.,3 = 46 1420 n.d. n.d. n.d. n.d. 140.9- DCDPSO powder phenylsulfide d50.sub.,3 = 328 143.1 2,4′-dichlorodi- 1.28 d903 = 1027 phenylsulfoxide Recryst- white 99.9 2,4′-dichlorodi- 0.1. n.d. <50 d10.sub.,3 = 29 68. n.d. n.d. n.d. 6.6 ± 143.3- DCDPSO powder phenylsulfoxide d50.sub.,3 = 55 0.4 144.6 d90.sub.,3 = 1415 CC- white 98.8 4,4′-dichlorodi- 0.2 0.50 <50 d10.sub.,3 = 231 72 763 874 1.13 9.6 ± 141.2- DCDPSO crystals phenylsulfide d50.sub.,3 = 497 0.4 144.9 according 2,4′-dichlorodi- 0.3 d90.sub.,3 = 863 to the phenylsulfoxide invention Recryst- white n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 142.8- DCDPSO crystals 144.1 CHCl.sub.3 Recryst- white n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 141.9- DCDPSOEA cystals 143.6

FIGURES AND REFERENCE SIGN LIST

(22) FIG. 1A shows the net of a prism with a symmetrical six-sided base surface bsu and a symmetrical six-sided top surface tsu and six side surfaces ssu1 to ssu6

(23) FIG. 1B shows the top view of the top surface tsu of an asymmetrical prism with a six-sided top surface tsu

(24) FIG. 1C shows the first side surface ssu of an asymmetrical six-sided prism

(25) FIG. 1D shows one embodiment of the geometry of the outer surface of the crystal C according to the invention

(26) FIG. 2A shows another embodiment of the geometry of the outer surface of the crystal C according to the invention

(27) FIG. 2B shows a photo taken with a light microscope of the geometry of the outer surface of the crystal C according to the invention with marked up edges and reference signs

(28) FIG. 3A shows a photo taken with a light microscope of the crystal composition CC showing crystals C (500 μm)

(29) FIG. 3B shows a photo taken with a light microscope of the crystal composition CC showing crystals C (200 μm)

(30) FIG. 4A shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form obtained from abcr GmbH (500 μm)

(31) FIG. 4B shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form obtained from abcr GmbH (200 μm)

(32) FIG. 5 shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form obtained from Alfa Aesar (500 μm)

(33) FIG. 6A shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form obtained from TCI GmbH (500 μm)

(34) FIG. 6B shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form obtained from TCI GmbH (1 mm)

(35) FIG. 7A shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form recrystallized from diethyl ether (500 μm)

(36) FIG. 7B shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form recrystallized form diethylether (200 μm)

(37) FIG. 8A illustrates the measurement of X.sub.c min

(38) FIG. 8B illustrates the measurement of X.sub.Fe max

(39) FIG. 9A shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form recrystallized from chloroform (200 μm)

(40) FIG. 9B shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form recrystallized from chloroform (500 μm)

(41) FIG. 10 shows a photo taken with a light microscope of 4,4′-dichlorodiphenylsulfoxide in particulate powder form recrystallized from ethyl acetate (500 μm) C crystal bsu six-sided base surface of the crystal (C) bsi1 first side of the six-sided base surface bsu bsi2 second side of the six-sided base surface bsu bsi3 third side of the six-sided base surface bsu bsi4 fourth side of the six-sided base surface bsu bsi5 fifth side of the six-sided base surface bsu bsi6 sixth side of the six-sided base surface bsu cb1 first corner of the six-sided base surface bsu cb2 second corner of the six-sided base surface bsu cb3 third corner of the six-sided base surface bsu cb4 fourth corner of the six-sided base surface bsu cb5 fifth corner of the six-sided base surface bsu cb6 sixth corner of the six-sided base surface bsu db diameter of the six-sided base surface bsu db14 shortest distance between the first corner cb1 and the fourth corner cb4 db25 shortest distance between the second corner cb2 and the fifth corner cb5 db36 shortest distance between the third corner cb3 and the sixth corner cb6 tsu six-sided top surface of the crystal C tsi1 first side of the six-sided top surface tsu tsi2 second side of the six-sided top surface tsu tsi3 third side of the six-sided top surface tsu tsi4 fourth side of the six-sided top surface tsu tsi5 fifth side of the six-sided top surface tsu tsi6 sixth side of the six-sided top surface tsu ct1 first corner of the six-sided top surface tsu ct2 second corner of the six-sided top surface tsu ct3 third corner of the six-sided top surface tsu ct4 fourth corner of the six-sided top surface tsu ct5 fifth corner of the six-sided top surface tsu ct6 sixth corner of the six-sided top surface tsu dt diameter of the six-sided top surface tsu dt14 shortest distance between the first corner ct1 and the fourth corner ct4 dt25 shortest distance between the second corner ct2 and the fifth corner ct5 dt36 shortest distance between the third corner ct3 and the sixth corner ct6 ssu1 first side surface of the crystal (C) ssu2 second side surface of the crystal (C) ssu3 third side surface of the crystal (C) ssu4 fourth side surface of the crystal (C) ssu5 fifth side surface of the crystal (C) ssu6 sixth side surface of the crystal (C) l1 length of the first side surface (ssu1) l2 length of the second side surface (ssu2) l3 length of the third side surface (ssu3) l4 length of the fourth side surface (ssu4) l5 length of the fifth side surface (ssu5) l6 length of the sixth side surface (ssu6) l11 shortest distance between the first corner ct1 and the first corner bt1 l22 shortest distance between the second corner ct2 and the second corner bt2 l33 shortest distance between the third corner ct3 and the third corner bt3 l44 shortest distance between the fourth corner ct4 and the fourth corner bt4 l55 shortest distance between the fifth corner ct5 and the fifth corner bt5 l66 shortest distance between the sixth corner ct6 and the sixth corner bt6