SULFONE POLYMER COMPOSITION, PREPARATION METHOD THEREOF AND THE THERMOPLASTIC MOLDING COMPOSITION THEREFROM

Abstract

A sulfone polymer composition and preparation method thereof, and thermoplastic molding composition therefrom, comprising: (A) at least one aromatic sulfone polymer; (B) one compound of 4,4′-dichlorodiphenyl sulfone; wherein, based on the total weight of the sulfone polymer composition, 4,4′-dichlorodiphenyl sulfone weight content is less than 600 ppm. In the preparation method, tetramethylene sulfone is used as a solvent, 4,4′-dichlorodiphenyl sulfone and 4,4′-Dihydroxydiphenyl sulfone or 4,4′-dihydroxy biphenyl are used as reactive monomers, while the mixed salt of sodium carbonate and potassium carbonate is used as salt-forming agent, the composition may be obtained by polymerization with solution polymerization techniques; wherein the molar ratio of the said potassium carbonate and sodium carbonate is 0.1: 100-5: 100. The sulfone polymer composition has a transmittance greater than 85%, a haze less than 4%, and a yellowness index less than 5, enjoying a significantly improved transparency and color levels.

Claims

1. A sulfone polymer composition, comprising: (A) an aromatic sulfone polymer; and (B) 4,4′- dichlorodiphenyl sulfone; wherein based on the total weight of the sulfone polymer composition, the weight content of the 4,4′-dichlorodiphenyl sulfone is less than 600 ppm.

2. The sulfone polymer composition according to claim 1, wherein the weight content of the said 4,4-dichlorodiphenyl sulfone is determined by headspace gas chromatography-mass spectrometry with an American CDS8000 Dynamic Headspace Concentrator headspace device having a headspace sampling chamber, enclosing traps filled with Tenax-GC organic adsorbing fillers, putting 0.2 g sulfone polymer composition to be tested into the headspace sampling chamber for one hour at 300° C., and testing the gas collected with Agilent's 7890B-5977A MSD type GC-MS monitoring equipment under chromatographic conditions of a capillary column of HP-5 MS, 30 m×250 μm, 0.25 m, wherein the temperature rises to 390° C. with the speed of 15° C./ min, the sample inlet temperature is 390° C., the carrier gas is He gas with a flow rate of 0.8 mL/min, with a split ratio of 50: 1 and MS conditions of EI source, ionizing voltage of 70 eV, ion source temperature of 250° C., and a scan range of 30-600 m/z.

3. The sulfone polymer composition according to claim 1, wherein based on the total weight of the sulfone polymer composition, the weight content of 4,4′-dichlorodiphenyl sulfone is less than 400 ppm.

4. The sulfone polymer composition according to claim 3, wherein based on the total weight of the sulfone polymer composition, the weight content of 4,4′-dichlorodiphenyl sulfone is less than 300 ppm.

5. The sulfone polymer composition according to claim 1, wherein the said sulfone polymer composition has a transmittance of greater than 85% and a haze of less than 4% obtained at the test made on an injection plastic plate with a thickness of 2 mm in accordance with ASTM D1003-07.

6. The sulfone polymer composition according to claim 1, wherein the said sulfone polymer composition has a Yellowness Index of less than 5 obtained at the test made on an injection plastic plate with a thickness of 2 mm in accordance with ASTM D1925.

7. The sulfone polymer composition according to claim 1, wherein the aromatic sulfone polymer is polyethersulfone, polyphenyl sulfone or mixtures thereof.

8. A preparation method for the sulfone polymer composition according to claim 1 comprising the following steps: using tetramethylene sulfone as a solvent, using 4,4′-dichlorodiphenyl sulfone and 4,4′-dihydroxydiphenyl sulfone or 4,4′-dihydroxybiphenyl as reactive monomers, using a mixed salt of sodium carbonate and potassium carbonate as a salt-forming agent, wherein the composition is obtained by polymerization with solution polymerization techniques, wherein when 4,4′-dichlorodiphenyl sulfone and 4,4′-dihydroxydiphenyl sulfone are used as reactive monomers, the polymer obtained will be polyethersulfone (PES) and the molar ratio of the said potassium carbonate and sodium carbonate is 0.1:100-3:100, and wherein when 4,4′-dichlorodiphenyl sulfone and 4,4′-dihydroxy biphenyl are used as reactive monomers, the polymer obtained will be polyphenyl sulfone (PPSU) and the molar ratio of the said potassium carbonate and sodium carbonate is 0.1:100-5:100.

9. A thermoplastic molding composition, comprising the sulfone polymer composition according to claim 1.

Description

DESCRIPTION OF FIGURES

[0028] FIG. 1 shows the viscosity growth curve of sulfone polymer prepared with salt forming agent of mixed salts in embodiment Example 1;

[0029] FIG. 2 shows the viscosity growth curve of sulfone polymer prepared with single salt forming agent in comparative Example 1;

[0030] FIG. 3 is a headspace GC-MS spectra of sulfone polymer prepared with salt forming agent of mixed salts in embodiment Example 1, wherein the mass spectral peak at 12.3min position is the residual monomer 4,4-dichlorodiphenyl sulfone;

[0031] FIG. 4 is a headspace GC-MS spectra of sulfone polymer prepared with single salt forming agent in comparative Example 1, wherein the mass spectral peak at 12.3min position is the residual monomer 4,4-dichlorodiphenyl sulfone.

EMBODIMENTS

[0032] The following specific embodiments further illustrate the present invention, the following examples are preferred embodiments of the present invention, but the embodiment of the present invention is not limited to those described below.

[0033] Testing Methods:

[0034] transmittance and haze: result of the test on a injection molding plate with a thickness of 2 mm according to ASTM D1003-07 (%).

[0035] Yellowness index: yellowness index obtained in the test on a injection molding plate with a thickness of 2 mm according to ASTM D1925 (YI).

[0036] Polymer melt viscosity growth: the melt viscosity may be monitored in a real-time way with a German MARIMEX company's VS-4450 on-line viscometer.

[0037] The weight content of 4,4′-dichlorodiphenyl sulfone is determined by headspace gas chromatography and mass spectrometry: with an American CDS8000 Dynamic Headspace Sampler concentrator headspace device, enclosing traps filled with Tenax-GC adsorbing organic fillers, put 0.2 g of polymer to be tested into the headspace sampling chamber for one hour at 300° C., test the gas collected gas with Agilent's 7890B-5977A MSD type GC-MS monitoring equipment; chromatographic conditions: capillary column of HP-5MS (30m×250 μm, 0.25 m); temperature rises to 390° C. with a speed of 15° C./min, inlet temperature of 390° C., the carrier gas is He gas with flow rate of 0.8 mL / min, split ratio 50: 1; mass spectrum conditions of El source, the ionization voltage of 70 eV, ion source temperature of 250° C., scanning range: 30-600 m/z. Internal standard method can be used to acquire the standard curve to quantify the content of the 4,4′-dichlorodiphenyl sulfone monomer.

EXAMPLE 1

[0038] Add sequentially 7.508 kg (30 mol) of 4,4′-dihydroxydiphenyl sulfone, 8.787 kg (30.6 mol) of 4,4′-dichlorodiphenyl sulfone into the 50L polymerization reactor equipped with a thermometer, a nitrogen-introducing tube, condensate trap, and a stirrer, then add to it 32.62 kg of tetramethylene sulfone, stir it and heat it to 100° C. to dissolve the monomer solution until transparency, and 3.396kg (32.039 mol) of salt-forming agent Na.sub.2CO.sub.3 and 132.6 g (0.961 mol) of salt-forming agent K.sub.2CO.sub.3, followed by addition of 2L of xylene, and heat it to start the salt forming reaction while stirring it continuously. The azeotrope forming from the water produced in the system and xylene is blown by the protective gas to the condensation tube, condensed therein and drops into water trap and layers there, the upper layer of xylene refluxes to the system; maintain a temperature range of 200° C. -210° C., when water amount collected is close to the theoretical value (540 g), let the reflux continue for 20 minutes, no water droplets falling being found indicating completion of the salt forming reaction. Distill it again and drain the xylene, and gradually heat it to 230° C. to start the polymerization reaction, and the viscosity detected starts to increase at this time. Keep it at constant temperature for 2.5 hours, the slope of viscosity growth curve is substantially zero, the viscosity growth curve is shown in FIG. 1. When the viscosity of the system becomes completely constant, the reaction will end; stop stirring and heating, pour the material slowly into deionized water and cool it into white striped solid, and then crush it into a powder with a pulverizer. Boil it with deionized water for 1 hour, filter it to remove the water, repeat so for 10 times, until the filtrate not becoming turbid when tested with silver nitrate, indicating that the powder byproduct salt has been washed clean. After filtration, put the polymer in a vacuum oven with 120° C. and dry it to constant weight and that is the product polyethersulfone (PES); the weight content of 4,4′- dichlorodiphenyl sulfone is determined by headspace gas chromatography—mass spectrometry, the detection chromatogram is shown in FIG. 3, the peak position appears in 12.8min position is mass spectrometry peak of the monomer 4,4′-dichlorodiphenyl sulfone. The test results of transmittance, yellowness index, haze and other performance indicators of the prepared sulfone polymer composition are shown in Table 1.

EXAMPLE 2

[0039] Based on Example 1, wherein except that then add to it 3.446kg (32.512 mol) of salt -forming agent Na.sub.2CO.sub.3 and 67.4 g (0.488 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 3

[0040] Based on Example 1, wherein except that then add to it 3.412 kg (32.195 mol) of salt-forming agent Na.sub.2CO.sub.3 and 111.242 g (0.805 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 4

[0041] Based on Example 1, wherein except that then add to it 3.429 kg (32.353 mol) of salt-forming agent Na.sub.2CO.sub.3 and 89.294 g (0.6470 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 5

[0042] Based on Example 1, wherein except that add to it3.463 kg (32.673 mol) of salt- forming agent Na.sub.2CO.sub.3 and 45.158 g (0.327 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 6

[0043] Based on Example 1, wherein except that then add to it 3.470 kg (32.738 mol) of salt-forming agent Na.sub.2CO.sub.3 and 36.198 g (0.262 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 7

[0044] Based on Example 1, wherein except that then add to it 3.480 kg (32.836 mol) of salt-forming agent Na.sub.2CO.sub.3 and 22.69 g (0.164 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 8

[0045] Based on Example 1, wherein except that then add to it 3.494 kg (32.967 mol) of salt-forming agent Na.sub.2CO.sub.3 and 4.56 g (0.0329 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

EXAMPLE 9

[0046] Based on Example 1, wherein except that add sequentially 5.586 kg (30 mol) of 4,4′-dihydroxybiphenyl sulfone , 8.787 kg (30.6 mol) of 4,4′- dichlorodiphenyl sulfone into the 50L polymerization reactor equipped with a thermometer, a nitrogen-introducing tube, condensate trap, and a stirrer, then add to it 28.14 kg of tetramethylene sulfone, stir it and heat it to dissolve, and then add to it 3.331 kg (31.428 mol) of salt-forming agent Na.sub.2CO.sub.3 and 0.217 kg (1.571 mol) of salt- forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 3 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyphenyl sulfone (PPSU), performance test results are shown in Table 1.

EXAMPLE 10

[0047] Based on Example 9, wherein except that then add to it 3.429 kg (32.353 mol) of salt-forming agent Na.sub.2CO.sub.3 and 893 g (0.647 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 9. Keep it at constant temperature for 3.5 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyphenyl sulfone (PPSU), performance test results are shown in Table 1.

EXAMPLE 11

[0048] Based on Example 9, wherein except that then add to it 3.495 kg (32.967 mol) of salt- forming agent Na.sub.2CO.sub.3 and 4.55 g (0.0329 mol) of salt-forming agent K.sub.2CO.sub.3, while the remaining is the same as in Example 9. Keep it at constant temperature for 4 hours to achieve completely constant system viscosity. After drying the polymer, the product obtained is polyphenyl sulfone (PPSU), performance test results are shown in Table 1.

COMPARATIVE EXAMPLE 1

[0049] Based on Example 1, wherein except that then add to it 3.498 kg (33 mol) of salt- forming agent Na.sub.2CO.sub.3, while the remaining is the same as in Example 1. Keep it at constant temperature for 4 hours, the slope of the viscosity growth curve shows a trend of slowing down, the viscosity growth curve is shown in FIG. 2, indicating that the viscosity has a constant tendency, and end the reaction. After drying the polymer, the product obtained is polyether sulfone (PES). The weight content of 4,4′-dichlorodiphenyl sulfone is determined by headspace gas chromatography—mass spectrometry, the detection chromatogram is shown in FIG. 4, the peak appears in 12.8 min position is MS peak of the monomer 4,4′-dichlorodiphenyl sulfone. The test results of performance are shown in Table 1.

COMPARATIVE EXAMPLE 2

[0050] Based on Example 9, wherein except that then add to it 3.498 kg (33 mol) of salt- forming agent Na.sub.2CO.sub.3, while the remaining is the same as in Example 9. Keep it at constant temperature for 4.5 hours, the system viscosity shows a constant trend, and end the reaction. After drying the polymer, the product obtained is polyphenyl sulfone (PPSU). The test results of performance are shown in Table 1.

COMPARATIVE EXAMPLE 3

[0051] Based on Example 1, wherein except that then add to it 3.496 kg (32.984 mol) of salt -forming agent Na.sub.2CO.sub.3 and 2.28 g (0.0165 mol) of salt-forming agent K.sub.2CO.sub.3, keep it at constant temperature for 4.5 hours while the remaining is the same as in Example 1. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

COMPARATIVE EXAMPLE 4

[0052] Based on Example 1, wherein except that then add to it 3.180 kg (33.0 mol of salt-forming agent Na.sub.2CO.sub.3 and 414.63 g (3 mol) of salt-forming agent K.sub.2CO.sub.3, keep it at constant temperature for 2.5 hours while the remaining is the same as in Example 1. After drying the polymer, the product obtained is polyethersulfone (PES), performance test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Performance test results of sulfone polymer composition in embodiment examples and comparative examples comp. comp. comp. comp. exmp. 1 exmp. 2 exmp. 3 exmp. 4 example 1 example 2 example 3 example 4 K.sub.2CO.sub.3:Na.sub.2CO.sub.3 (mol ratio) 0:100 0:100 0.05:100 10:100 3:100 1.5:100 2.5:100 2:100 Melt viscosity/cP .Math. g/cm3 298 578 311 488 323 350 344 341 4,4′-dichlorodiphenyl 988 879 949 1078 229 155 285 328 sulfone content/ppm Transmittance/% 77.6 75.8 75.3 71.2 88.4 87.5 88.5 86.1 Yellowness index 14.65 15.54 15.11 13.24 2.56 2.76 2.67 3.27 Haze/% 8.56 7.07 7.58 8.42 2.45 2.13 2.85 3.25 example example example 5 example 6 example 7 example 8 example 9 10 11 K.sub.2CO.sub.3:Na.sub.2CO.sub.3 (mol ratio) 1:100 0.8:100 0.5:100 0.1:100 5:100 2:100 0.1:100 Melt viscosity/cP .Math. g/cm3 372 387 399 413 633 655 643 4,4′-dichlorodiphenyl 389 438 496 586 189 387 405 sulfone content/ppm Transmittance/% 86.4 85.1 85.9 85.5 87.2 86.5 85.1 Yellowness index 3.29 3.33 4.68 4.89 3.84 4.76 4.87 Haze/% 3.07 3.74 3.65 3.92 3.26 3.57 3.75