A method for preparing polyphenylene sulfide film

Abstract

The present invention discloses a method for preparing a polyphenylene sulfide film. The raw materials of the polyphenylene sulfide film include: polyphenylene sulfide resin, phthalate, paraffin wax, 1,4-cyclohexanediol terephthalate, talcum powder, benzophenone, and a metal-organic framework / polyaniline composite; the raw materials are mixed, extruded after melt blending by a twin-screw extruder, and the melting temperature is 290 °C; then, it is cooled and shaped by a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; the obtained sheet is subjected to biaxial stretching, first longitudinally stretched in the length direction, and then transversely stretched in the width direction. The method of the present invention obtains a polyphenylene sulfide film that simultaneously satisfies a high melting temperature and a high elongation at break.

Description

Technical Field

[0001] The present invention relates to the technical field of polyphenylene sulfide, and particularly relates to a method for preparing a polyphenylene sulfide film. Background Art

[0002] High-performance polyphenylene sulfide films have excellent chemical resistance and thermal stability at high temperatures, and have flame retardancy, insulation, radiation resistance, and good mechanical properties. The application methods of this material have always been the goal of continuous exploration by researchers in various countries. Polyphenylene sulfide films have excellent heat resistance, flame retardancy, rigidity, chemical reagent resistance, excellent electrical insulation, and low hygroscopicity, and are particularly suitable for use in electrical and electronic instruments, mechanical components, automotive components, etc.

[0003] In recent years, high-performance polyphenylene sulfide films have been widely used, especially in occasions with relatively high requirements for environmental conditions, such as humid environments, environments where chemical agents are easily corroded, and even ionizing radiation environments. At the same time, it is also used as an electronic sealing material for electronic components, and can also be used as a sealing material for mechanical seals and the food packaging industry. For this reason, many researchers are working hard to seek the research and development of polyphenylene sulfide films. However, characteristics such as relatively low melting temperature and elongation at break of polyphenylene sulfide films limit their application range. In order to change these characteristics, it is necessary to perform certain treatments on polyphenylene sulfide films, especially the synthesis of polyphenylene sulfide resins. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing a polyphenylene sulfide film, which is used to solve the problem that the elongation at break and melting temperature of polyphenylene sulfide films are not high.

[0005] The present invention is achieved by the following technical solutions:

[0006] A method for preparing a polyphenylene sulfide film, the raw materials of the polyphenylene sulfide film include: polyphenylene sulfide resin, phthalate, paraffin, 1,4-cyclohexanediol terephthalate, talcum powder, benzophenone, and metal-organic framework / polyaniline composite; the raw materials are mixed, melt-blended by a twin-screw extruder and then extruded, and the melting temperature is 290 °C; then it is cooled and shaped by a chill roll and an electrostatic adsorption device, so that the melt becomes a sheet with high flatness and low crystallinity; the obtained sheet is subjected to biaxial stretching, first longitudinally stretched in the length direction, and then transversely stretched in the width direction.

[0007] Further, the content of the metal-organic framework / polyaniline composite is 3-10 parts.

[0008] Further, the content of the metal-organic framework / polyaniline composite is 7-10 parts.

[0009] Further, the content of the metal-organic framework / polyaniline composite is 10 parts.

[0010] Further, the preparation method of the metal-organic framework / polyaniline composite is as follows: Add FeCl3·6H2O and terephthalic acid into N,N-dimethylformamide, stir, heat to 150 °C, and then maintain at 150 °C for 12 h; then, naturally cool to room temperature, filter to obtain a precipitate, then wash the precipitate three times with ethanol, then wash three times with distilled water, and then dry the precipitate at 150 °C for 8 h; Take the dried precipitate and add it to an acidic aqueous solution, adjust the pH value of the aqueous solution to be acidic with HCl, cool the solution to 0 °C while stirring, add polyaniline, and stir for 20 min, then slowly dropwise add 20 mL of ammonium persulfate aqueous solution; then continue to stir the mixed solution at 0 °C for 24 h, then filter to obtain a precipitate, wash the precipitate three times with ethanol, and then wash three times with distilled water to obtain the metal-organic framework / polyaniline composite.

[0011] Further, the method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching roller, stretch in the longitudinal direction of the sheet, the stretching temperature is 90 °C, the stretching ratio is 2.5 times, and then cool with a 20 °C cooling roller.

[0012] Further, the method of transverse stretching is as follows: Feed the sheet into the transverse stretching roller, stretch in the transverse direction of the sheet, the preheating temperature is 90 °C, and preheat for 20 s; the stretching temperature is 90 °C, and the stretching ratio is 2.5 times; then relax in width while performing heat setting, the heat setting temperature is 140 °C, the time is 12 s, the relaxation rate is 2%, after cooling to room temperature, obtain the polyphenylene sulfide film.

[0013] Further, the polyphenylene sulfide film, by weight, comprises: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 1 - 10 parts of the metal-organic framework / polyaniline composite.

[0014] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0015] By adding the metal-organic framework / polyaniline to polyphenylene sulfide, mixing the raw materials, extruding through a twin-screw extruder after melt blending, the melting temperature is 290 °C; then cooling and shaping with a chill roll and an electrostatic adsorption device, making the melt into a sheet with high flatness and low crystallinity; performing biaxial stretching on the obtained sheet, first longitudinally stretching in the length direction, and then transversely stretching in the width direction, a polyphenylene sulfide film that simultaneously meets the high melting temperature and high elongation at break is obtained. Specific Embodiments

[0016] To make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with embodiments. The illustrative embodiments and descriptions of the present invention are only used to explain the present invention and are not intended to limit the present invention.

[0017] The preparation method of the metal-organic framework / polyaniline composite in the present invention is as follows:

[0018] 1.0 g of FeCl3·6H2O and 0.5 g of terephthalic acid are added to 70 mL of N,N-dimethylformamide, stirred for 30 min, heated to 150 °C, and then maintained at 150 °C for 12 h; then, it is naturally cooled to room temperature, the precipitate is filtered, and the precipitate is washed three times with ethanol, then washed three times with distilled water, and then the precipitate is dried at 150 °C for 8 h; 0.4 g of the dried precipitate is added to 150 mL of an acidic aqueous solution, the pH value of the aqueous solution is adjusted to be acidic with HCl, the solution is cooled to 0 °C while stirring, 0.2 mL of polyaniline is added, and stirred for 20 min, then 20 mL of an ammonium persulfate aqueous solution is slowly added dropwise, where the concentration of the ammonium sulfate solution is 0.025 g / mL; then the mixed solution is continuously stirred at 0 °C for 24 h, then the precipitate is filtered, the precipitate is washed three times with ethanol, and then washed three times with distilled water to obtain the metal-organic framework / polyaniline composite.

[0019] The preparation method of the metal-organic framework compound in the present invention is as follows:

[0020] 1.0 g of FeCl3·6H2O and 0.5 g of terephthalic acid are added to 70 mL of N,N-dimethylformamide, stirred for 30 min, heated to 150 °C, and then maintained at 150 °C for 12 h; then, it is naturally cooled to room temperature, the precipitate is filtered, and the precipitate is washed three times with ethanol, then washed three times with distilled water, and then the precipitate is dried at 150 °C for 8 h to obtain the metal-organic framework compound.

[0021] Example 1

[0022] A preparation method of a polyphenylene sulfide film

[0023] The polyphenylene sulfide film includes, by weight: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 1 part of metal-organic framework / polyaniline composite;

[0024] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, and the melting temperature is 290°C; then cool and shape with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first longitudinally stretch in the length direction, and then transversely stretch in the width direction.

[0025] The method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching roll, stretch it longitudinally in the sheet, the stretching temperature is 90°C, the stretching ratio is 2.5 times, and then cool it with a 20°C cooling roll.

[0026] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching roll, stretch it transversely in the sheet, the preheating temperature is 90°C, and preheat for 20 s; the stretching temperature is 90°C, the stretching ratio is 2.5 times; then relax in the width direction while performing heat setting, the heat setting temperature is 140°C, the time is 12 s, the relaxation rate is 2%, and after cooling to room temperature, a polyphenylene sulfide film is obtained.

[0027] Example 2

[0028] A preparation method of polyphenylene sulfide film

[0029] The polyphenylene sulfide film includes, by weight: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talc powder, 5 parts of benzophenone, and 3 parts of metal-organic framework / polyaniline composite

[0030] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, and the melting temperature is 290°C; then cool and shape with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first longitudinally stretch in the length direction, and then transversely stretch in the width direction.

[0031] The method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching roll, stretch it longitudinally in the sheet, the stretching temperature is 90°C, the stretching ratio is 2.5 times, and then cool it with a 20°C cooling roll.

[0032] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching roll, stretch it transversely in the sheet, the preheating temperature is 90°C, and preheat for 20 s; the stretching temperature is 90°C, the stretching ratio is 2.5 times; then relax in the width direction while performing heat setting, the heat setting temperature is 140°C, the time is 12 s, the relaxation rate is 2%, and after cooling to room temperature, a polyphenylene sulfide film is obtained.

[0033] Example 3

[0034] A preparation method of polyphenylene sulfide film

[0035] The polyphenylene sulfide film includes, by weight parts: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 5 parts of metal-organic framework / polyaniline composite;

[0036] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, and the melting temperature is 290°C; then cool and shape them with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first longitudinally stretch in the length direction, and then transversely stretch in the width direction.

[0037] The method of longitudinal stretching is: Feed the sheet into the longitudinal stretching roll, stretch it longitudinally in the sheet, the stretching temperature is 90°C, the stretching ratio is 2.5 times, and then cool it with a 20°C cooling roll.

[0038] The method of transverse stretching is: Feed the sheet into the transverse stretching roll, stretch it transversely in the sheet, the preheating temperature is 90°C, and preheat for 20 s; the stretching temperature is 90°C, the stretching ratio is 2.5 times; then relax in the width direction while performing heat setting, the heat setting temperature is 140°C, the time is 12 s, the relaxation rate is 2%, and after cooling to room temperature, the polyphenylene sulfide film is obtained.

[0039] Example 4

[0040] A preparation method of polyphenylene sulfide film

[0041] The polyphenylene sulfide film includes, by weight parts: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 7 parts of metal-organic framework / polyaniline composite;

[0042] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, and the melting temperature is 290°C; then cool and shape them with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first longitudinally stretch in the length direction, and then transversely stretch in the width direction.

[0043] The method of longitudinal stretching is: Feed the sheet into the longitudinal stretching roll, stretch it longitudinally in the sheet, the stretching temperature is 90°C, the stretching ratio is 2.5 times, and then cool it with a 20°C cooling roll.

[0044] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching rollers, stretch it in the transverse direction of the sheet, with a preheating temperature of 90 °C and a preheating time of 20 s; the stretching temperature is 90 °C and the stretching ratio is 2.5 times; then relax it in width while performing heat setting, with a heat setting temperature of 140 °C and a time of 12 s, and a relaxation rate of 2%. After cooling to room temperature, a polyphenylene sulfide film is obtained.

[0045] Example 5

[0046] A method for preparing a polyphenylene sulfide film

[0047] The polyphenylene sulfide film described above, by weight, includes: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 10 parts of metal-organic framework / polyaniline composite;

[0048] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, with a melting temperature of 290 °C; then cool and shape them with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first stretch it longitudinally in the length direction, and then stretch it transversely in the width direction.

[0049] The method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching rollers, stretch it in the longitudinal direction of the sheet, with a stretching temperature of 90 °C and a stretching ratio of 2.5 times, and then cool it with a 20 °C cooling roll.

[0050] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching rollers, stretch it in the transverse direction of the sheet, with a preheating temperature of 90 °C and a preheating time of 20 s; the stretching temperature is 90 °C and the stretching ratio is 2.5 times; then relax it in width while performing heat setting, with a heat setting temperature of 140 °C and a time of 12 s, and a relaxation rate of 2%. After cooling to room temperature, a polyphenylene sulfide film is obtained.

[0051] Comparative Example 1

[0052] A method for preparing a polyphenylene sulfide film

[0053] The polyphenylene sulfide film described above, by weight, includes: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone;

[0054] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, with a melting temperature of 290 °C; then cool and shape them with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first stretch it longitudinally in the length direction, and then stretch it transversely in the width direction.

[0055] The method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching rollers, stretch it in the longitudinal direction of the sheet, with a stretching temperature of 90 °C and a stretching ratio of 2.5 times, and then cool it with a 20 °C cooling roller.

[0056] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching rollers, stretch it in the transverse direction of the sheet, with a preheating temperature of 90 °C and a preheating time of 20 s; the stretching temperature is 90 °C and the stretching ratio is 2.5 times; then relax it in width while performing heat setting, with a heat setting temperature of 140 °C, a time of 12 s, a relaxation rate of 2%, and after cooling to room temperature, a polyphenylene sulfide film is obtained.

[0057] Comparative Example 2

[0058] A method for preparing a polyphenylene sulfide film

[0059] The polyphenylene sulfide film described above, by weight, comprises: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 5 parts of metal-organic framework compound;

[0060] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, with a melting temperature of 290 °C; then cool and shape them with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first stretch it longitudinally in the length direction, and then stretch it transversely in the width direction.

[0061] The method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching rollers, stretch it in the longitudinal direction of the sheet, with a stretching temperature of 90 °C and a stretching ratio of 2.5 times, and then cool it with a 20 °C cooling roller.

[0062] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching rollers, stretch it in the transverse direction of the sheet, with a preheating temperature of 90 °C and a preheating time of 20 s; the stretching temperature is 90 °C and the stretching ratio is 2.5 times; then relax it in width while performing heat setting, with a heat setting temperature of 140 °C, a time of 12 s, a relaxation rate of 2%, and after cooling to room temperature, a polyphenylene sulfide film is obtained.

[0063] Comparative Example 3

[0064] A method for preparing a polyphenylene sulfide film

[0065] The polyphenylene sulfide film described above, by weight, comprises: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talcum powder, 5 parts of benzophenone, and 5 parts of polyaniline;

[0066] The preparation method is as follows: Mix the raw materials, extrude them after melt blending through a twin-screw extruder, and the melting temperature is 290 °C; then cool and shape them with a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; perform biaxial stretching on the obtained sheet, first longitudinally stretch in the length direction, and then transversely stretch in the width direction.

[0067] The method of longitudinal stretching is as follows: Feed the sheet into the longitudinal stretching rolls, stretch it longitudinally on the sheet, the stretching temperature is 90 °C, the stretching ratio is 2.5 times, and then cool it with a 20 °C cooling roll.

[0068] The method of transverse stretching is as follows: Feed the sheet into the transverse stretching rolls, stretch it transversely on the sheet, the preheating temperature is 90 °C, and preheat for 20 s; the stretching temperature is 90 °C, the stretching ratio is 2.5 times; then relax in the width direction while performing heat setting, the heat setting temperature is 140 °C, the time is 12 s, the relaxation rate is 2%, and after cooling to room temperature, a polyphenylene sulfide film is obtained.

[0069] Test Example 1

[0070] Fusing temperature: Test according to the method of GB / T19466-2004.

[0071] Compressive strength: Test the compressive strength in the thickness direction using a compressive strength tester according to the method of GB / T1041-2008.

[0072] Elongation at break: Test according to the method of GB / T1040.3.

[0073] Table 1 Performance Test

[0074]

[0075] It can be seen from the data in Table 1 that when the metal-organic framework / polyaniline composite is added, the fusing temperature of the polyphenylene sulfide film is increased, and at the same time, good elasticity is maintained.

[0076] The above specific embodiments have further detailed the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a polyphenylene sulfide film, characterized in that, The polyphenylene sulfide film comprises, by weight parts: 50 parts of polyphenylene sulfide resin, 5 parts of phthalate, 5 parts of paraffin, 5 parts of 1,4-cyclohexanediol terephthalate, 1 part of talc powder, 5 parts of benzophenone, and 5 - 10 parts of metal-organic framework / polyaniline composite; the raw materials are mixed, melt-blended and extruded through a twin-screw extruder, and the melting temperature is 290°C; then it is cooled and shaped by a chill roll and an electrostatic adsorption device to make the melt into a sheet with high flatness and low crystallinity; the obtained sheet is biaxially stretched, first longitudinally stretched in the length direction, and then transversely stretched in the width direction; The metal-organic framework / polyaniline composite is obtained by reacting a metal-organic framework with polyaniline in an acidic condition by adding ammonium persulfate; The preparation method of the metal-organic framework / polyaniline composite is as follows: Add FeCl3·6H2O and terephthalic acid into N,N-dimethylformamide, stir, heat to 150°C, and then maintain at 150°C for 12 h; then, naturally cool to room temperature, filter to obtain a precipitate, then wash the precipitate three times with ethanol, then wash three times with distilled water, and then dry the precipitate at 150°C for 8 h; take the dried precipitate and add it to an acidic aqueous solution, adjust the pH value of the aqueous solution to be acidic with HCl, cool the solution to 0°C while stirring, add polyaniline, and stir for 20 min, then slowly dropwise add 20 mL of ammonium persulfate aqueous solution; then continue to stir the mixed solution at 0°C for 24 h, then filter to obtain a precipitate, wash the precipitate three times with ethanol, and then wash three times with distilled water to obtain the metal-organic framework / polyaniline composite.

2. The preparation method according to claim 1, characterized in that, The content of the metal-organic framework / polyaniline composite is 7 - 10 parts.

3. The preparation method according to claim 1, characterized in that, The content of the metal-organic framework / polyaniline composite is 10 parts.

4. The preparation method according to claim 1, characterized in that, The method of longitudinal stretching is as follows: Feed the sheet into longitudinal stretching rollers, stretch it longitudinally on the sheet, the stretching temperature is 90°C, the stretching ratio is 2.5 times, and then cool it with a 20°C cooling roll.

5. The preparation method according to claim 1, characterized in that, The method of transverse stretching is as follows: Feed the sheet into transverse stretching rollers, stretch it transversely on the sheet, the preheating temperature is 90°C, and preheat for 20 s; the stretching temperature is 90°C, and the stretching ratio is 2.5 times; then relax in the width direction while performing heat setting, the heat setting temperature is 140°C, the time is 12 s, the relaxation rate is 2%, after cooling to room temperature, the polyphenylene sulfide film is obtained.

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