POLYPHENYLENE SULFONE

Abstract

A polyphenylene sulfone (PPSU) consisting essentially of benzophenone coupled phenylene sulfone segments A and B of formula (I) wherein segments A and B can be same or different and are of formula (II) wherein x is an integer of from 4.5 to 8.

##STR00001##

Claims

1-16. (canceled)

17. A polyphenylene sulfone (PPSU) consisting essentially of benzophenone coupled phenylene sulfone segments A and B of formula I ##STR00004## wherein segments A and B can be same or different and are of formula II ##STR00005## wherein x is from 4.5 to 9.

18. The polyphenylene sulfone according to claim 17 wherein x is from 4.5 to 7.

19. The polyphenylene sulfone according to claim 17 which is linear.

20. A solution comprising the polyphenylene sulfone according to claim 17.

21. A solution according to claim 20 comprising N-methyl-2-pyrrolidone, dimethylacetamide and/or sulfolane.

22. A process for making the polyphenylene sulfone according to claim 17 comprising reacting at least one dihalodiphenylsulfone with at least one dihydroxybiphenyl to give phenylene sulfone oligomers of a number average degree of polymerization in the range from 4.5 to 9 and reacting said oligomers with at least one dihalobenzophenone.

23. The process according to claim 22, wherein the reacting step is carried out as a one-pot reaction.

24. The process according to claim 22, wherein the reacting step is carried out in the presence of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylacetamide and/or sulfolane.

25. The process according to claim 24, comprising filtering a solution at above room temperature, wherein the solution comprises a polyphenylene sulfone (PPSU) consisting essentially of benzophenone coupled phenylene sulfone segments A and B of formula I ##STR00006## wherein segments A and B can be same or different and are of formula II ##STR00007## wherein x is of from 4.5 to 9.

26. A method for manufacture of a coating, film, fiber, foam, membrane, or molded article, wherein the manufacturing comprises a polyphenylene sulfone according to claim 17.

27. A method for manufacture of a coating, film, fiber, foam, membrane, or molded article, wherein the manufacturing comprises a polyphenylene sulfone obtained from the process according to claim 22.

28. A method for manufacturing a coating, film, fiber, or membrane, wherein the manufacturing comprises the solution according to claim 20.

29. A method for manufacturing a membrane comprising the method of claim 26.

30. A membrane comprising at least one polyphenylene sulfone according to claim 17.

31. An article comprising a membrane according to claim 29.

32. A method of water purification comprising the membrane according to claim 30.

33. A method for fracking or recycling of desalinated water on oil platforms comprising the water purified by the method according to claim 32.

Description

EXAMPLES

[0060] The examples below provide further explanation of the invention, but do not restrict the same.

Definitions and Abbreviations:

[0061] Reaction time: time during which the reaction mixture was kept at 190° C. [0062] DCDPS: 4,4′-dichlorodiphenylsulfone [0063] BP: 4,4′-dihydroxybiphenyl [0064] NMP: N-methyl-2-pyrrolidone

[0065] The particle size of the potassium carbonate was determined at a suspension of the solid in chlorobenzene/sulfolane 60/40 (by weight) using a Malvern Mastersizer 2000 instrument as described above.

[0066] The chain length x of the oligomers was determined by potentiometic titration of the OH groups and elemental analysis of the organic Cl-content of the precipitated and dried sample taken from the reactor prior to the addition of 4,4′-dichlorobenzophenone. The calculated values correspond to the number average molecular weight of the oligomer.

[0067] The time required for filtering the polymer solutions was determined.

[0068] The obtained polymers were processed into granules using a ZSK 18-extruder. The throughput was 2.5 kg/h at 300 rpm, the melt temperature, measured with a thermometer directly in the melt cake was below 385° C. From the so obtained granules ISO-bars (80 mm×10 mm×4 mm) and S2-tensile bars were prepared at a mass temperature of 370° C. and a tool temperature of 140° C.

[0069] The solution viscosity (V.N.) was determined using a solution of 0.01 g/ml polymer in N-methylpyrrolidone at 25° C. (DIN EN ISO 1628-1 (October 2012)).

[0070] The glass transition temperatures (Tg) and the melting points (Tm) of the polymers were determined by DSC analysis with a heating rate of 20 K/min. The figures reported for the glass transition temperature, the melting point and the melting heat are the values determined in the 2nd heating run.

[0071] The melt stability of the samples was determined using a capillary rheometer at a mass temperature of 400° C. for 60 minutes. Thereby the apparent viscosity of the melt was determined at a shear rate of 55 s.sup.−1 every 5 minutes. The quotient (Q) of the apparent viscosity determined at 60 minutes over the apparent viscosity determined at 5 minutes is a measure for the melt stability.

[0072] The resistance of the products against hydraulics fluids, petrol and/or fuel was determined as resistance against Skydrol® LD4 (58 wt % tributyl phosphate, 20-30 wt % dibutylphenyl phosphate, 5-10 wt % butyldiphenyl phosphate, 1-5 wt % 2,6-di-terbutyl-p-kresol, less than 10 wt % carboxylate). S2-tensile bars were stored in Skydrol® LD4 for 24 hours. In each case 2 of the S2-tensile bars were bent to a bending radius of 132 mm using a stencil prior to storing them. Using a camera, a picture was taken every minute to determine the time until break.

[0073] The results of the measurements are given in Table 1.

[0074] Preparation of the Polymers—General Procedural Measures used in Each Case

[0075] A vessel equipped with a stirrer, Dean-Stark-trap, nitrogen-inlet and temperature control was used. 304.05 g (2.20 mol) potassium carbonate with a volume average particle size of 34.5 μm was used. The water that was formed in the reaction was continuously removed by distillation. An azeotrope former was not employed. Lost NMP was replaced.

[0076] After the reaction time, 1500 ml NMP were added to the vessel and the temperature of the reaction mixture was adjusted to 135° C. Then methyl chloride was added to the vessel for 60 minutes. Then nitrogen was purged through the reaction mixture for another 30 minutes. The reaction mixture was then cooled to 80° C. and was then transferred into a heated pressure filter (80° C.) to separate the potassium chloride formed in the reaction mixture by filtration.

[0077] Filtration was carried out at a nitrogen pressure of 2.0 bar, using a filter of a pore size of 3 μm.

[0078] The polymers were isolated from the filtrate by precipitating the filtrate into a bath of desalinated water at room temperature (falling distance 0.5 m, throughput appr. 2.5 l/h). The obtained pearls were collected and washed with water at 85° C. for 20 h (water throughput 160 l/h) Thereafter the pearls were dried at a temperature below the glass transition temperature. The residual moisture content was less than 0.1 wt-%.

[0079] Small amounts of materials were precipitated for those samples which could not be filtered. Thereafter they were washed with water and dried at 120° C. for 24 h. The residual moisture content was less than 0.1 wt-%.

Comparative Copolymer C1

[0080] In the vessel 522.63 g (1.82 mol) of DCDPS, 372.41 g (2.00 mol) of BP, 50.22 g (0.20 mol) 4,4′-dichlorobenzophenone, and the potassium carbonate were dissolved respectively suspended in 1152 ml NMP in a nitrogen atmosphere.

[0081] The mixture was heated to 190° C. within one hour. Thereafter, the reaction time was 5 h.

[0082] Filtration took 8 h.

[0083] The polymer was then isolated from the filtrate and dried.

Comparative Copolymer C2

[0084] In the vessel 522.63 g (1.82 mol) of DCDPS, 372.41 g (2.00 mol) of BP, and the potassium carbonate were dissolved respectively suspended in 952 ml NMP in a nitrogen atmosphere.

[0085] The mixture was heated to 190° C. within one hour. The initial reaction time was 70 minutes.

[0086] Thereafter, 20 ml of the suspension were separated. Then, 50.22 g (0.200 mol) of 4,4′-dichlorobenzophenone dissolved in 200 ml NMP were charged to the vessel. At 190° C. the reaction was continued. The reaction time was 4h.

[0087] Filtration took 8.5 h.

[0088] The obtained polymer was then isolated and dried.

Comparative Copolymer C3

[0089] In the vessel 508.28 g (1.77 mol) of DCDPS, 372.41 g (2.00 mol) of BP, 62.78 g (0.25 mol) of 4,4′-dichlorobenzophenone, and the potassium carbonate were dissolved respectively suspended in 1152 ml NMP in a nitrogen atmosphere.

[0090] The mixture was heated to 190° C. within one hour. The reaction time was 5 h.

[0091] Filtration took 10 h.

[0092] The polymer was then isolated from the filtrate and dried.

PPSU 1

[0093] In the vessel 508.28 g (1.77 mol) of DCDPS, 372.41 g (2.00 mol) of BP, and the potassium carbonate were dissolved respectively suspended in 952 ml NMP in a nitrogen atmosphere.

[0094] The mixture was heated to 190° C. within one hour. The initial reaction time was 70 minutes.

[0095] Thereafter, 20 ml of the suspension were separated. Then, 62.78 g (0.250 mol) of 4,4′-dichlorobenzophenone dissolved in 200 ml NMP were charged to the vessel.

[0096] At 190° C. the reaction was continued. The reaction time was 4 h.

[0097] Filtration took 7.5 h.

[0098] The polymer was then isolated from the filtrate and dried.

Comparative Example C4

[0099] In the vessel 493.92 g (1.72 mol) of DCDPS, 372.41 g (2.00 mol) of BP, 75.33 g (0.3 mol) of 4,4′-dichlorobenzophenone, and the potassium carbonate were dissolved respectively suspended in 1152 ml NMP in a nitrogen atmosphere.

[0100] The mixture was heated to 190° C. within one hour. The reaction time was 5.5 h.

[0101] Filtration took 12 h.

[0102] The polymer was then isolated from the filtrate and dried.

PPSU 2

[0103] In the vessel 493.92 g (1.72 mol) of DCDPS, 372.41 g (2.00 mol) of BP, and the potassium carbonate were dissolved respectively suspended in 952 ml NMP in a nitrogen atmosphere.

[0104] The mixture was heated to 190° C. within one hour. The initial reaction time was 70 minutes.

[0105] Thereafter, 20 ml of the suspension were separated. Then, 75.33 g (0.30 mol) of 4,4′-dichlorobenzophenone dissolved in 200 ml NMP were charged to the vessel. At 190° C. the reaction was continued. The reaction time was 5 h.

[0106] Filtration took 8 h.

[0107] The polymer was then isolated from the filtrate and dried.

Comparative Copolymer C5

[0108] In the vessel 465.20 g (1.62 mol) of DCDPS, 372.41 g (2.00 mol) of BP, 100.44 g (0.4 mol) of 4,4′-dichlorobenzophenone, and were dissolved respectively suspended in 1152 ml NMP in a nitrogen atmosphere.

[0109] The mixture was heated to 190° C. within one hour. The reaction time was 6 h.

[0110] Filtration took 14 h.

[0111] The polymer which could be obtained was then isolated from the filtrate and dried.

PPSU 3

[0112] In the vessel 465.20 g (1.62 mol) of DCDPS, 372.41 g (2.00 mol) of BP, and the potassium carbonate were dissolved respectively suspended in 952 ml NMP in a nitrogen atmosphere.

[0113] The mixture was heated to 190° C. within one hour. The initial reaction time was 70 minutes.

[0114] Thereafter, 20 ml of the suspension were separated. Then, 100.44 g (0.40 mol) of 4,4′-dichlorobenzophenone dissolved in 200 ml NMP were charged to the vessel. At 190° C. the reaction was continued. The reaction time was 5.5 h.

[0115] Filtration took 10 h.

[0116] The polymer was then isolated from the filtrate and dried.

Comparative Copolymer C6

[0117] In the vessel 450.86 g (1.57 mol) of DCDPS, 372.41 g (2.00 mol) of BP, and the potassium carbonate were dissolved respectively suspended in 952 ml NMP in a nitrogen atmosphere.

[0118] The mixture was heated to 190° C. within one hour. The initial reaction time was 70 minutes.

[0119] Thereafter, 20 ml of the suspension were separated. Then, 113.00 g (0.45 mol) of 4,4′-dichlorobenzophenone dissolved in 200 ml NMP were charged to the vessel. At 190° C. the reaction was continued. The reaction time was 6 h.

[0120] Even after a filtration time of 24 h only a minor part of the solution was filtered.

[0121] After 24 h the solution became a gel, and precipitation was only possible after diluting 20 ml solution/gel with 20 ml NMP and heating up to 120° C.

[0122] The polymer which could be obtained was then isolated from the filtrate and dried.

Comparative Copolymer C7

[0123] In the vessel 450.86 g (1.57 mol) of DCDPS, 372.41 g (2.00 mol) of BP, 113.00 g (0.45 mol) of 4,4′-dichlorobenzophenone, and the potassium carbonate were dissolved respectively suspended in 1152 ml NMP in a nitrogen atmosphere.

[0124] The mixture was heated to 190° C. within one hour. The reaction time was 6 h.

[0125] Even after a filtration time of 24 h only a minor part of the solution was filtered. After 24 h the solution became a gel, and precipitation was only possible after diluting 20 ml solution/gel with 20 ml NMP and heating up to 120° C.

[0126] The polymer which could be obtained was then isolated from the filtrate and dried.

[0127] As can be seen from the results of the measurements given below in Table 1 that for the PPSU consisting essentially of benzophenone coupled segments of a chain length x in the range of 4.5 to 9 the properties aimed at could be observed. At higher chain lengths the resistance against Skydrol® was not given. At lower chain lengths the samples could not be processed in an easy way.

TABLE-US-00002 TABLE 1 Example C1 C2 C3 1 C4 2 C5 3 C6.sup.a) C7.sup.a) C8.sup.b) CI-BPO [mol-% 9.9 9.9 12.4 12.4 14.9 14.9 19.8 19.8 22.3 22.3 based on CI- Monomers], charged Reaction 5 h 70 min 5 h 70 min 5.5 h 70 min 6.5 h 70 min 70 min 6 h modus 4 h 4 h 5 h 5.5 h 6 h Filtration [h] 8 8.5 10 7.5 12 8 14 10 >24 >24 <6 Chain length — 4290 — 3290 — 2710 — 2130 1820 — — segments [g/mol] Chain length — 10.25 — 7.75 — 6.30 — 4.85 4.08 — — segments x VN 68.5 69.3 72.9 70.7 67.1 68.2 66.2 65.3 — — 71.6 [ml/g] Tg [° C.] 211 210 207 207 206 205 205 202 201 200 219 Tm [° C.] — — — — — — — 298 299 ΔHm [J/g] — — — — — — — 2.9 5.2 Skydrol <2 <1 5 >24 >24 >24 >24 >24 — — <2 Res. [h] Q 1.5 1.6 1.6 1.5 1.8 1.4 1.6 1.4 — — 1.3 Appearance Tr..sup.c) Tr. Tr. Tr. Tr. Tr. — Tr. — — Tr. Plate .sup.a)no homogeneous solution for viscosity measurements in NMP was obtained .sup.b)Polyphenylene ether sulfone not derived from benzophenone monomers (commercially available from BASF SE, Ultrason ® P 3010) .sup.c)Transparent