CN115386118A - Preparation method of polyphenylene sulfide biaxially oriented film - Google Patents
Preparation method of polyphenylene sulfide biaxially oriented film Download PDFInfo
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- CN115386118A CN115386118A CN202211136898.6A CN202211136898A CN115386118A CN 115386118 A CN115386118 A CN 115386118A CN 202211136898 A CN202211136898 A CN 202211136898A CN 115386118 A CN115386118 A CN 115386118A
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 99
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 238000005266 casting Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000011265 semifinished product Substances 0.000 claims abstract description 6
- 238000010345 tape casting Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 230000037303 wrinkles Effects 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 6
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- 230000008676 import Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 229920006269 PPS film Polymers 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000000465 moulding Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention relates to the technical field of special engineering plastics, and discloses a preparation method of a polyphenylene sulfide biaxially oriented film, which comprises the following steps: (1) Adding the polyphenylene sulfide resin particles into an extruder for melt extrusion, and carrying out tape casting to obtain a polyphenylene sulfide initial tape casting film; (2) Longitudinally stretching the polyphenylene sulfide initial casting film by 2-6 times at 120-220 ℃, and transversely stretching by 2-6 times at 120-220 ℃ to obtain a polyphenylene sulfide biaxially oriented film semi-finished product; (3) And carrying out heat treatment on the semi-finished product of the polyphenylene sulfide biaxially oriented film to obtain the polyphenylene sulfide biaxially oriented film. The invention adopts the polyphenylene sulfide resin improved by the organic solvent as the raw material, has low salt content and volatile component content, is easy to obtain, and gets rid of the phenomenon that the raw material depends on import abroad; the polyphenylene sulfide resin film subjected to high-temperature biaxial stretching treatment has high crystallinity, smooth surface, no wrinkles and good stretching performance, and the thickness of the prepared biaxial stretching film can reach 5-50 mu m.
Description
Technical Field
The invention relates to the technical field of special engineering plastics, in particular to a preparation method of a polyphenylene sulfide biaxially oriented film.
Background
The polyphenylene sulfide (PPS) has a structure that benzene rings and sulfur atoms are alternately connected, a molecular chain has high rigidity and regularity, and the polyphenylene sulfide is a semi-crystalline polymer and has high strength, modulus and excellent combustion performance; the PPS product has good creep resistance, lower linear expansion coefficient, good dimensional stability and smaller molding shrinkage. The polyphenylene sulfide shows extremely excellent heat resistance in all thermoplastic engineering plastics, the melting point is as high as 280-290 ℃, the polyphenylene sulfide begins to decompose in air at a temperature of more than 400-430 ℃, the polyphenylene sulfide is stable in air or nitrogen at a temperature of less than 400 ℃, the polyphenylene sulfide basically has no mass loss, and the heat stability is far higher than that of engineering plastics such as PA, PBT, PET, POM and the like; polyphenylene sulfide has excellent chemical corrosion resistance, the chemical corrosion resistance is second to that of polytetrafluoroethylene, and almost no solvent can be dissolved below 200 ℃; the polyphenylene sulfide resin has extremely low water absorption rate, small volume resistivity change under high temperature and high humidity conditions, and small change of dielectric constant with temperature and frequency, so that the polyphenylene sulfide resin is suitable for products with extremely strict electrical property requirements, and is an excellent electrical insulating material. Therefore, polyphenylene sulfide is widely used in the fields of electronics, automobile industry, machinery industry, military industry, textile industry, aviation, and the like, due to its excellent properties.
Polyphenylene sulfide is used as a semi-crystalline thermoplastic material, and conditions are created for preparing the biaxially oriented film. However, the existing biaxial stretching film technology is mostly mastered in foreign enterprises, production equipment needs to be imported, the equipment cost is extremely high, and the foreign enterprises limit the sale of the PPS pure resin in China, so that domestic enterprises do not have proper technology to develop the PPS film with excellent performance.
Disclosure of Invention
In view of this, the invention provides a preparation method of a polyphenylene sulfide biaxially oriented film, so as to solve the problem that the polyphenylene sulfide biaxially oriented film with excellent comprehensive properties cannot be prepared in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a polyphenylene sulfide biaxially oriented film comprises the following steps:
(1) Adding the polyphenylene sulfide resin particles into an extruder for melt extrusion, and carrying out tape casting to obtain a polyphenylene sulfide initial tape casting film;
(2) Longitudinally stretching the polyphenylene sulfide initial casting film by 2-6 times at 120-220 ℃, and transversely stretching by 2-6 times at 120-220 ℃ to obtain a polyphenylene sulfide biaxially oriented film semi-finished product;
(3) And carrying out heat treatment on the semi-finished product of the polyphenylene sulfide biaxially oriented film to obtain the polyphenylene sulfide biaxially oriented film.
Preferably, in the preparation method of the polyphenylene sulfide biaxially oriented film, the polyphenylene sulfide resin is modified by an organic solvent, and the melt index of the polyphenylene sulfide resin is 80-200g/10min.
Preferably, in the above method for preparing a biaxially oriented polyphenylene sulfide film, the method for improving a polyphenylene sulfide resin is as follows:
heating and stirring polyphenylene sulfide resin and an organic solvent at 60-120 ℃, filtering, adding water into the filtrate, heating and stirring at 120-200 ℃, filtering, drying, extruding and granulating to obtain the polyphenylene sulfide resin.
Preferably, in the above method for preparing a polyphenylene sulfide biaxially oriented film, the organic solvent includes N-methylpyrrolidone, dimethyl formaldehyde, dimethylacetamide, 1, 3-dimethylimidazolidinone, hexamethylphosphoramide, a nitrogen-containing organic compound, sulfoxide-sulfone solvents, ketone solvents, ether solvents, halogen-based solvents, alcohol solvents, and phenol solvents.
Preferably, in the preparation method of the polyphenylene sulfide biaxially oriented film, the melt extrusion temperature in the step (1) is 280-320 ℃, and more preferably 290-310 ℃.
Preferably, in the preparation method of the polyphenylene sulfide biaxially oriented film, the extruder is a single-screw or double-screw extruder, and the length-diameter ratio of the screw is 40-60; more preferably, the screw length to diameter ratio is 45 to 52.
Preferably, in the above method for preparing a biaxially oriented polyphenylene sulfide film, the longitudinal stretching in step (2) is stretching 3 to 5 times at 140 to 180 ℃; the transverse stretching is 3-5 times at 150-180 ℃.
Preferably, in the above method for preparing a biaxially oriented polyphenylene sulfide film, the stretching speed in step (2) is 10 to 30m/min.
Preferably, in the above method for preparing a polyphenylene sulfide biaxially oriented film, the longitudinal stretching and the transverse stretching in step (2) are performed synchronously or asynchronously.
Preferably, in the preparation method of the polyphenylene sulfide biaxially oriented film, the heat treatment temperature in the step (3) is 170-250 ℃, and the heat treatment time is 10-120s; further preferably, the heat treatment temperature is 180 to 220 ℃.
Preferably, in the above method for producing a biaxially oriented polyphenylene sulfide film, the heat treatment in the step (3) is a stepwise temperature increase treatment comprising
First-stage heat treatment: treating at 170-200 deg.C for 5-60s;
second stage heat treatment: treating at 200-250 deg.C for 5-60s.
The invention provides a preparation method of a polyphenylene sulfide biaxially oriented film, which has the following beneficial effects compared with the prior art:
the invention adopts the polyphenylene sulfide resin improved by the organic solvent as the raw material, has low salt content and volatile component content, is easy to obtain, and gets rid of the phenomenon that the raw material depends on import abroad;
the polyphenylene sulfide resin film subjected to high-temperature biaxial stretching treatment has high crystallinity, smooth surface, no wrinkles and good stretching performance, and the thickness of the prepared biaxial stretching film can reach 5-50 mu m.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment provides a preparation method of a polyphenylene sulfide resin biaxially oriented film, wherein the preparation method of the improved polyphenylene sulfide resin comprises the following steps:
adding 60L of dimethyl sulfoxide into a 200L reaction kettle, adding 12kg of 3514PPS (melt index of 140g/10 min) produced by Xinjiang province and finished material Co., ltd, heating to 120 ℃, stirring for 2h, discharging slurry, filtering a solvent, washing a filter cake with deionized water for 2 times, adding the filter cake into the 200L reaction kettle, adding 100L of deionized water, heating to 200 ℃, stirring for 6h, discharging the slurry, filtering, and drying the raw materials in a boiling type drying box; putting the dried raw materials into a double-screw extruder with the diameter of 45mm and the length-diameter ratio of 48, vacuumizing at an exhaust hole under 0.08MPa, and performing grain pumping to obtain the improved polyphenylene sulfide resin.
Example 1
Adding modified polyphenylene sulfide resin with the melt index of 80g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =48, melting at 300 ℃, filtering through a filter screen with the diameter of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.7mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 1000mm and the temperature of 30 ℃, longitudinally stretching the casting film by 3.0 times at 140 ℃ to obtain a longitudinally stretched film, transversely stretching by 3.0 times at 150 ℃, treating at 180 ℃ for 10s, and treating at 220 ℃ for 5s to obtain the flat PPS film without wrinkles.
Example 2
Adding an improved polyphenylene sulfide resin with a melt index of 120g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =40, melting at 280 ℃, filtering through a filter screen with the diameter of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.7mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 800mm and the temperature of 30 ℃, longitudinally stretching the casting film by 4.2 times at 120 ℃ to obtain a longitudinally stretched film, transversely stretching by 4.0 times at 180 ℃, treating at 195 ℃ for 5s, and treating at 240 ℃ for 10s to obtain a flat PPS film without wrinkles.
Example 3
Adding an improved polyphenylene sulfide resin with a melt index of 200g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =50, melting at 320 ℃, filtering through a filter screen with the thickness of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.8mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 1000mm and the temperature of 30 ℃, longitudinally stretching the casting film by 2.0 times at 200 ℃ to obtain a longitudinally stretched film, transversely stretching by 3.0 times at 220 ℃, treating at 200 ℃ for 10s, and treating at 250 ℃ for 5s to obtain a flat PPS film without wrinkles.
Example 4
Adding an improved polyphenylene sulfide resin with a melt index of 140g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =60, melting at 290 ℃, filtering through a filter screen with the thickness of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.8mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 800mm and the temperature of 30 ℃, longitudinally stretching the casting film by 4.5 times at 120 ℃ to obtain a longitudinally stretched film, transversely stretching by 5 times at 150 ℃, treating at 170 ℃ for 10s, and treating at 220 ℃ for 5s to obtain a flat PPS film without wrinkles.
Comparative example 1
Untreated commercially available polyphenylene sulfide resin (3514 PPS (melt index of 140g/10 min) from Zhejiang Xin & materials Ltd.) was fed into a single screw extruder having a screw diameter of 65mm and a melt index of 140g/10min, and was melted at 300 ℃ and filtered through a screen of about 10 μm, and then was molded through a T-shaped port having a width of 950mm and a thickness of 0.7mm to form a cast film, which was sufficiently cooled on a cooling roll having a diameter of 1000mm and a temperature of 30 ℃, and the cast film was longitudinally stretched at 140 ℃ by a factor of 3.0 to give a longitudinally stretched film, which was further transversely stretched at 150 ℃ by a factor of 3.0, treated at 180 ℃ for 10 seconds, and further treated at 220 ℃ for 5 seconds to give a PPS film which was free of wrinkles and flat.
The PPS films prepared in the above examples 1-4 and comparative examples were tested for their performance according to the following methods:
1. thickness of film
The thickness of the test piece is measured by a measuring tool with plane upper and lower sides specified in the measuring mechanical method for the thickness of the plastic film and the thin sheet of GB 6672. Measuring three points in the gauge length according to the thickness of each sample, and taking an arithmetic mean value; the thickness is accurate to 0.001mm.
2. Tensile strength and elongation
The tensile strength and the elongation at break of the film are tested by GB/T1040.1-2018 and GB/T1040.3-2018 standards, the test speed is 50mm/min, a cutting method is adopted to prepare a sample, the type of the sample is 2, a strip with the length of 150mm and the width of (15 +/-0.1) mm is adopted, the gauge length is 50mm, the test speed is (250 +/-25) mm/min, and the longitudinal tensile performance and the transverse tensile performance are respectively tested.
3. Melting point determination
And (3) heating the mixture from 30 to 320 ℃ for heat preservation minutes at the speed of 20 ℃/min by adopting 8500DSC of platinum Elmer, cooling the mixture to 50 ℃ at the speed of 20 ℃/min, heating the mixture to 320 ℃ at the speed of 20 ℃/min, and measuring the melting point of the film.
The results of the performance tests are shown in table 1.
Table 1 examples 1-4 performance test results
As shown in Table 1, the polyphenylene sulfide stretched film prepared by the invention has smooth surface, no wrinkles and good stretching performance, is suitable for continuous production, and can reach the thickness of less than 50 μm.
In addition, the invention researches the performance of the polyphenylene sulfide biaxial stretching film from the factors of longitudinal stretching temperature, ratio, transverse stretching temperature, ratio and the like.
1. Influence of longitudinal stretching temperature on properties of polyphenylene sulfide biaxially oriented film
Adding an improved polyphenylene sulfide resin with a melt index of 80g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =48, melting at 300 ℃, filtering through a filter screen with the diameter of about 10 mu M, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.7mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 1000mm and the temperature of 30 ℃, longitudinally stretching the casting film by 3.0 times at the temperature M to obtain a longitudinally stretched film, transversely stretching the casting film by 3.0 times at the temperature of 150 ℃, treating at 180 ℃ for 10s, and treating at 220 ℃ for 5s to obtain the flat PPS film without wrinkles.
In the above procedure, M was set to 110 ℃, 120 ℃, 150 ℃, 180 ℃, 220 ℃ and 230 ℃ in this order as test examples 1 to 6, respectively, and the properties of the PPS biaxially oriented films obtained in test examples 1 to 6 were measured, and the test results are shown in Table 2.
Table 2 test examples 1-6 results of performance test
As can be seen from table 2, when the stretching temperature is too low, the rigidity of the material casting film is too strong to stretch, and a stretched film cannot be obtained, when the temperature is too high, the casting film is in a semi-molten state, the process is difficult to control during stretching, and the film wrinkles; the optimum temperature for longitudinal stretching is 120-220 degrees.
2. Influence of transverse stretching temperature on properties of polyphenylene sulfide biaxially oriented film
Adding an improved polyphenylene sulfide resin with a melt index of 80g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =48, melting at 300 ℃, filtering through a filter screen with the diameter of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.7mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 1000mm and the temperature of 30 ℃, longitudinally stretching the casting film by 3.0 times at 140 ℃ to obtain a longitudinally stretched film, transversely stretching by 3.0 times at N temperature, treating at 180 ℃ for 10s, and treating at 220 ℃ for 5s to obtain the flat PPS film without wrinkles.
In the above procedure, N was set to 110 ℃, 120 ℃, 150 ℃, 180 ℃, 220 ℃ and 230 ℃ in this order as test examples 7 to 12, respectively, and the properties of the PPS biaxially oriented films obtained in test examples 7 to 12 were measured, and the test results are shown in Table 3.
TABLE 3 test examples 7-12 Performance test results
From the above table, when the stretching temperature is too low, the rigidity of the material casting film is too strong to stretch, and a biaxially stretched film cannot be obtained, when the temperature is too high, the casting film is in a semi-molten state, the process is difficult to control during stretching, and the film wrinkles, and the optimum temperature for transverse stretching is 120-220 ℃.
3. Influence of longitudinal stretching ratio on performance of polyphenylene sulfide biaxial stretching film
Adding an improved polyphenylene sulfide resin with a melt index of 80g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =48, melting at 300 ℃, filtering through a filter screen with the diameter of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.7mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 1000mm and the temperature of 30 ℃, longitudinally stretching the casting film by X times at 140 ℃ to obtain a longitudinally stretched film, transversely stretching by 3.0 times at 150 ℃, treating at 180 ℃ for 10s, and treating at 220 ℃ for 5s to obtain a flat PPS film without wrinkles.
In the above procedure, X was set to 2 times, 3 times, 5 times, 6 times and 7 times in this order as test examples 13 to 17, respectively, and the properties of the PPS biaxially oriented films obtained in test examples 13 to 17 were measured, and the results of the measurement are shown in Table 4.
TABLE 4 test examples 13 to 17 Performance test results
From the above table, it can be seen that the stretching ratio is too low, the performance of the material cannot be well exerted, the stretching ratio is too high, the film is broken by pulling, the film is difficult to form, and the optimal stretching ratio is 2-6 times; meanwhile, if the draw ratio in the longitudinal and transverse directions is too different, the film has a remarkable anisotropic appearance, which may affect the application of the film.
4. Influence of transverse stretching multiplying power on performance of polyphenylene sulfide biaxial stretching film
Adding an improved polyphenylene sulfide resin with a melt index of 80g/10min into a single-screw extruder with a screw diameter of 65mm and an L/D =48, melting at 300 ℃, filtering through a filter screen with the diameter of about 10 mu m, then molding through a T-shaped opening with the width of 950mm and the thickness of 0.7mm to form a casting film, fully cooling the casting film on a cooling roller with the diameter of 800mm and the temperature of 30 ℃, longitudinally stretching the casting film by 3.0 times at 140 ℃ to obtain a longitudinally stretched film, transversely stretching by Y times at 150 ℃, treating at 180 ℃ for 10s, and treating at 220 ℃ for 5s to obtain a flat PPS film without wrinkles.
In the above procedure, Y was set to 2 times, 3 times, 5 times, 6 times and 7 times in this order as test examples 18 to 22, respectively, and the properties of the PPS biaxially oriented films obtained in test examples 18 to 22 were measured, and the results of the measurement are shown in Table 5.
TABLE 5 test examples 18 to 22 Performance test results
As can be seen from the above table, when the polyphenylene sulfide material is longitudinally stretched and then transversely stretched, the stretching ratio cannot be too large, the film is easily released from the fixture due to the too large stretching ratio, the required clamping force is greatly increased, the requirement on equipment is increased, and the performance of the material is not greatly improved; meanwhile, the longitudinal stretching ratio and the transverse stretching ratio are too different, so that the anisotropy of the film is easily increased, and the application of the film is influenced.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed in the embodiment, the method corresponds to the method disclosed in the embodiment, so the description is simple, and the relevant points can be referred to the description of the method part.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the polyphenylene sulfide biaxially oriented film is characterized by comprising the following steps:
(1) Adding the polyphenylene sulfide resin particles into an extruder for melt extrusion, and carrying out tape casting to obtain a polyphenylene sulfide initial tape casting film;
(2) Longitudinally stretching the polyphenylene sulfide initial casting film by 2-6 times at 120-220 ℃, and transversely stretching by 2-6 times at 120-220 ℃ to obtain a polyphenylene sulfide biaxially oriented film semi-finished product;
(3) And carrying out heat treatment on the semi-finished product of the polyphenylene sulfide biaxially oriented film to obtain the polyphenylene sulfide biaxially oriented film.
2. The method for preparing the polyphenylene sulfide biaxially oriented film according to claim 1, wherein the polyphenylene sulfide resin is an organic solvent-modified polyphenylene sulfide resin, and the melt index of the polyphenylene sulfide resin is 80 to 200g/10min.
3. The method for preparing the polyphenylene sulfide biaxially oriented film according to claim 2, wherein the improvement method of the polyphenylene sulfide resin is as follows:
heating and stirring polyphenylene sulfide resin and an organic solvent at 60-120 ℃, filtering, adding water into the filtrate, heating and stirring at 120-200 ℃, filtering, drying, extruding and granulating to obtain the polyphenylene sulfide resin.
4. The method for preparing a biaxially oriented polyphenylene sulfide film according to claim 2 or 3, wherein the organic solvent comprises N-methylpyrrolidone, dimethyl formaldehyde, dimethylacetamide, 1, 3-dimethylimidazolidinone, hexamethylphosphoramide, a nitrogen-containing organic compound, a sulfoxide-sulfone solvent, a ketone solvent, an ether solvent, a halogen-based solvent, an alcohol solvent, or a phenol solvent.
5. The method for preparing polyphenylene sulfide biaxially oriented film according to claim 1, wherein the melt extrusion temperature in step (1) is 280 to 320 ℃.
6. The method for preparing the polyphenylene sulfide biaxially oriented film according to claim 1, wherein the extruder is a single-screw or twin-screw extruder, and the length-diameter ratio of the screws is 40-60.
7. The method for preparing the polyphenylene sulfide biaxially oriented film according to claim 1, wherein the longitudinal stretching in the step (2) is stretching at 140 to 180 ℃ by 3 to 5 times; the transverse stretching is 3-5 times at 150-180 ℃; the stretching speed of the longitudinal stretching and the stretching speed of the transverse stretching are both 10-30m/min.
8. The method for preparing the polyphenylene sulfide biaxially oriented film according to claim 1, wherein the longitudinal stretching and the transverse stretching in step (2) are performed synchronously or asynchronously.
9. The method for preparing the polyphenylene sulfide biaxially oriented film according to claim 1, wherein the heat treatment temperature in the step (3) is 170 to 250 ℃ and the heat treatment time is 10 to 120 seconds.
10. The method for preparing a polyphenylene sulfide biaxially oriented film according to claim 1, wherein the heat treatment in the step (3) is a stepwise temperature rise treatment comprising
First-stage heat treatment: treating at 170-200 deg.C for 5-60s;
second-stage heat treatment: treating at 200-250 deg.C for 5-60s.
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| CN116478434A (en) * | 2023-05-09 | 2023-07-25 | 深圳市宇田新材料科技有限公司 | Preparation method of antibacterial polyphenylene sulfide film |
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