AMORPHOUS POLYMER (P) COMPRISING SEGMENTS (S1), (S2) AND (S3)

Abstract

The present invention relates to an amorphous polymer (P) comprising segments (S1) containing a sulfone group, segments (S2) containing a ketone group and segments (S3) containing a polyarylene group. Moreover, the present invention relates to a process for the preparation of said amorphous polymer (P), a composition comprising the amorphous polymer (P) and an article comprising the amorphous polymer (P).

Claims

1.-18. (canceled)

19. An amorphous polymer (P) comprising ##STR00003## wherein the amorphous polymer (P) comprises 80.1 to 89% by mol of segments (S1) and 11 to 19.9% by mol of segments (S2), based on the total number of mols of segments (S1) and segments (S2) comprised in the amorphous polymer (P).

20. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) comprises repeat units (RU1) obtainable by the reaction between at least one aromatic dihalogen compound (D1,1) comprising the segment (S1), and at least one aromatic dihydroxy compound (aDHy1).

21. The amorphous polymer (P) according to claim 20, wherein the aromatic dihalogen compound (D1,1) is at least one compound selected from the group consisting of 4,4′-dihalogendiphenylsulfone and 4,4′-bis[(4-chlorophenyl)sulfonyl]-1,1′-biphenyl.

22. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) comprises repeat units (RU2) obtainable by the reaction between at least one dihalogen compound (D2,1) comprising the segment (S2) and at least one aromatic dihydroxy compound (aDHy2).

23. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) has a polydispersity (Q) in the range of 2.0 to ≤5.0.

24. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) has an average molecular weight (M.sub.w) in the range of 30,000 to 120,000 g/mol, measured using gel permeation chromatography (GPC), wherein dimethylacetamide (DMAc) is used as solvent and narrowly distributed polymethyl methacrylate is used as standard in the measurement.

25. The amorphous polymer (P) according to claim 22, wherein the dihalogen compound (D2,1) is 4,4′-dihalogen benzophenone.

26. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) comprises repeat units (RU3) obtainable by the reaction between at least one aromatic dihydroxy compound (D2,2) comprising the segment (S2) and at least one aromatic dihalogen compound (aDHa1).

27. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) comprises repeat units (RU4) obtainable by the reaction between at least one aromatic dihydroxy compound (D3,1), comprising the segment (S3) and at least one aromatic dihalogen compound (aDHa2).

28. The amorphous polymer (P) according to claim 19, wherein the aromatic dihydroxy compound (aDHy1) or (aDHy2) is 4,4′-biphenol.

29. The amorphous polymer (P) according to claim 19, wherein the amorphous polymer (P) comprises repeat units (RU1) and (RU2), wherein the repeat units (R1) are obtainable by the reaction between at least one aromatic dihalogen compound (D1,1) comprising the segment (S1), and at least one aromatic dihydroxy compound (aDHy1), and wherein the repeat units (RU2) are obtainable by the reaction between at least one dihalogen compound (D2,1) comprising the segment (S2) and at least one aromatic dihydroxy compound (aDHy2), wherein the amorphous polymer (P) comprises no other repeat units than repeat units (RU1) and (RU2).

30. The amorphous polymer (P) according to claim 20, wherein the repeat units (RU1) are obtained by the reaction of the monomers 4,4′-dichlorodiphenylsulfone and 4,4′-biphenol.

31. The amorphous polymer (P) according to claim 22, wherein the repeat units (RU2) are obtained by the reaction of the monomers 4,4′-dichlorobenzophenone and 4,4′-biphenol.

32. A process for the preparation of the amorphous polymer (P) according to claim 19, by converting a reaction mixture (R.sub.G) comprising as components: (A1) at least one aromatic dihalogen sulfone compound (D1,1), (A2) at least one aromatic dihalogen ketone compound (D2,1), (B1) 4,4′-biphenol, (C) at least one carbonate component comprising at least 80% by weight of potassium carbonate, based on the overall weight of component (C) in the reaction mixture (R.sub.G), (D) at least one aprotic polar solvent.

33. A composition comprising the amorphous polymer (P) according to claim 19.

34. An article comprising the amorphous polymer (P) according to claim 19.

35. The article according to claim 34, wherein it is selected from the group consisting of a fitting, pipe, a valve, a manifold, an aircraft interior panel or component, a cookware, a medical instrument or part of instrument, a medical case or tray, a laboratory animal cage, a laboratory equipment, a coating, a composite, a fiber and a fabric.

36. The article according to claim 34, wherein the article is transparent.

Description

EXAMPLES

[0152] Components Used

[0153] DCDPS: 4,4′-dichlorodiphenyl sulfone,

[0154] DCBPO: 4,4′-dichlorobenzophenone,

[0155] BP: 4,4′-biphenol,

[0156] Potassium carbonate: K.sub.2CO.sub.3; anhydrous; volume-average particle size of 34.5 μm,

[0157] NMP: N-methylpyrrolidone,

[0158] PPSU: polyphenylensulfone (ULTRASON® P 3010)

[0159] General Procedures

[0160] The viscosity number of the polymers is determined in a 1% solution in NMP at 25° C., according to DIN EN ISO 1628-1.

[0161] The isolation of the polymers is carried out by dripping an NMP solution of the polymers in demineralized water at room temperature (25° C.). The drop height is 0.5 m, the throughput is about 2.5 I/h. The beads obtained are then extracted with water (water throughput 160 I/h) at 85° C. for 20 h. The beads are dried at 150° C. for 24 h (hours) at reduced pressure (<100 mbar) to a residual moisture of below 0.1% by weight.

[0162] The obtained amorphous polymers (P) were granulated via a ZSK 18 extruder. The throughput was 2.5 kg/h at a rotation speed of 300 rpm, the temperature of the melt was measured with an inserting thermometer at a melt cake and was below 385° C.

[0163] The granules obtained were injection molded at a mass temperature of 370° C. and a mold temperature of 140° C. to obtain ISO bars (80*10*4 mm*mm*mm) and S2 tensile bars.

[0164] The melt stability of the samples was measured at a mass temperature of 400° C., using a capillary rheometer over a period of 60 minutes. Therefore, every five minutes the apparent viscosity of the melt was measured at an apparent shear rate of 55 s.sup.−1. The melt stability is the quotient of the apparent viscosity after 60 minutes divided by the apparent viscosity after 5 minutes. The results are shown in table 1.

[0165] The glass transition temperature (T.sub.g) and the melting point of the obtained products is determined via differential scanning calorimetry DSC at a heating ramp of 20 K/min in the second heating cycle as described above.

[0166] The content of benzophenone groups is measured by .sup.1H-NMR using CDCl.sub.3 as solvent.

[0167] The resistance of the polymer against hydraulic fluids, petrol and/or fuel was determined as resistance against Skydrol® LD4 (58 wt.-% tributyl phosphate, 20 to 30 wt.-% dibutylphenyl phosphate, 5 to 10 wt.-% butylphenyl phosphate, 1 to 5 wt.-% 2,6-di-terbutyl-p-kresol, less than 10 wt.-% carboxalate). S2-pullrods were stored in Skydrol® LD4 for 24 hours. In each case, two of the S2-pullrods 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.

[0168] Polymer V1

[0169] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 522.63 g (1.82 mol) of DCDPS, 372.41 g (2.00 mol) of 4,4′-dihydroxybiphenyl, 50.22 g (0.20 mol) 4,4′-dichlorobenzophenone, and 304.05 g (2.20 mol) of potassium carbonate with a volume average particle size of 34.5 μm were suspended in 1152 ml NMP in a nitrogen atmosphere.

[0170] The mixture was heated to 190° C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190° C. The water that was formed in the reaction was continuously removed by distillation, lost NMP was replaced.

[0171] At 190° C. the reaction was continued for another 5 h, then 1500 ml NMP were added to the reactor and the temperature of the suspension was adjusted to 135° C. (took 10 minutes). Then Methylchloride was added to the reactor for 60 minutes. Then N.sub.2 was purged through the suspension for another 30 minutes. The solution was then cooled to 80° C. and was then transferred into a pressure filter to separate the potassium chloride formed in the reaction by filtration. 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).

[0172] Amorphous Polymer (P) 2

[0173] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 508.28 g (1.77 mol) of DCDPS, 372.41 g (2.00 mol) of 4,4′-dihydroxybiphenyl, 62.78 g (0.25 mol) of 4,4′-dichlorobenzophenone, and 304.05 g (2.20 mol) of potassium carbonate with a volume average particle size of 34.5 μm were suspended in 1152 ml NMP in a nitrogen atmosphere.

[0174] The mixture was heated to 190° C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190° C. The water that was formed in the reaction was continuously removed by distillation, lost NMP was replaced.

[0175] At 190° C. the reaction was continued for another 5 h, then 1500 ml NMP were added to the reactor and the temperature of the suspension was adjusted to 135° C. (took 10 minutes). Then Methylchloride was added to the reactor for 60 minutes. Then N.sub.2 was purged through the suspension for another 30 minutes. The solution was then cooled to 80° C. and was then transferred into a pressure filter to separate the potassium chloride formed in the reaction by filtration. 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).

[0176] Amorphous Polymer (P) 3

[0177] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 493.92 g (1.72 mol) of DCDPS, 372.41 g (2.00 mol) of 4.4′-dihydroxybiphenyl, 75.33 g (0.3 mol) of 4,4′-dichlorobenzophenone, and 304.05 g (2.20 mol) of potassium carbonate with a volume average particle size of 34.5 μm were suspended in 1152 ml NMP in a nitrogen atmosphere.

[0178] The mixture was heated to 190° C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190° C. The water that was formed in the reaction was continuously removed by distillation, lost NMP was replaced.

[0179] At 190° C. the reaction was continued for another 5.5 h, then 1500 ml NMP were added to the reactor and the temperature of the suspension was adjusted to 135° C. (took 10 minutes). Then Methylchloride was added to the reactor for 60 minutes. Then N.sub.2 was purged through the suspension for another 30 minutes. The solution was then cooled to 80° C. and was then transferred into a pressure filter to separate the potassium chloride formed in the reaction by filtration. 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).

[0180] Amorphous Polymer (P) 4

[0181] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 465.22 g (1.62 mol) of DCDPS, 372.41 g (2.00 mol) of 4,4′-dihydroxybiphenyl, 100.44 g (0.40 mol) of 4,4′-dichlorobenzophenone, and 304.05 g (2.20 mol) of potassium carbonate with a volume average particle size of 34.5 μm were suspended in 1152 ml NMP in a nitrogen atmosphere.

[0182] The mixture was heated to 190° C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190° C. The water that was formed in the reaction was continuously removed by distillation, lost NMP was replaced.

[0183] At 190° C. the reaction was continued for another 6 h, then 1500 ml NMP were added to the reactor and the temperature of the suspension was adjusted to 135° C. (took 10 minutes). Then Methylchloride was added to the reactor for 60 minutes. Then N.sub.2 was purged through the suspension for another 30 minutes. The solution was then cooled to 80° C. and was then transferred into a pressure filter to separate the potassium chloride formed in the reaction by filtration. 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).

[0184] Polymer V5

[0185] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 450.86 g (1.57 mol) of DCDPS, 372.41 g (2.00 mol) of 4,4′-dihydroxybiphenyl, 113.00 g (0.45 mol) of 4,4′-dichlorobenzophenone, and 304.05 g (2.20 mol) of potassium carbonate with a volume average particle size of 34.5 μm were suspended in 1152 ml NMP in a nitrogen atmosphere.

[0186] The mixture was heated to 190° C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190° C. The water that was formed in the reaction was continuously removed by distillation, lost NMP was replaced.

[0187] At 190° C. the reaction was continued for another 6 h, then 1500 ml NMP were added to the reactor and the temperature of the suspension was adjusted to 135° C. (took 10 minutes). Then Methylchloride was added to the reactor for 60 minutes. Then N.sub.2 was purged through the suspension for another 30 minutes. The solution was then cooled to 80° C. and was then transferred into a pressure filter to separate the potassium chloride formed in the reaction by filtration. 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).

TABLE-US-00001 TABLE 1 Example V1 2 3 4 V5 PPSU Filtration time 8 10 12 14 >24 n.d. [h] Content 8.7 11.2 14.0 18.7 21* 0 BPO-units [mol %] VZ 68.5 72.9 67.1 68.9 Not sol. 71.6 [ml/g] in NMP Tg [° C.] 211 207 206 205 200 219 Tm [° C.] none none none none 299 ΔHm [J/g] 0 0 0 0 5.2 Skydrol <2 5 >24 >24 <2 Res. [h] Q 1.5 1.6 1.8 1.6 n.d. 1.3 Appearance trans- trans- trans- trans- opaque trans- Plate parent parent parent parent parent *Solution not completely homogeneous

[0188] As can be seen from the results given in table 1, if the content of benzophenone units (BPO units) is below 10 mol %, no improvement of the Skydrol-resistance can be detected. If the content of BPO-based units is above 20 mol %, the product can not be isolated since the filtration of the suspension takes more than 24 h. If a small amount of material is precipitated and washed, no homogeneous solution in NMP for V.N. measurements is possible. In CDCl.sub.3 (H-NMR) the product is also not completely soluble, nevertheless the obtained spectra allow to determine the content of BPO-based units. A small amount of the product isolated from trial V5 was melt pressed at 320° C. to a thin film. Even though the film thickness was only 50 μm, the sample was opaque.