CN110894291B - Aromatic polyoxadiazole film and preparation method thereof - Google Patents
Aromatic polyoxadiazole film and preparation method thereof Download PDFInfo
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- CN110894291B CN110894291B CN201911250628.6A CN201911250628A CN110894291B CN 110894291 B CN110894291 B CN 110894291B CN 201911250628 A CN201911250628 A CN 201911250628A CN 110894291 B CN110894291 B CN 110894291B
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000005266 casting Methods 0.000 claims abstract description 35
- 230000015271 coagulation Effects 0.000 claims abstract description 19
- 238000005345 coagulation Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 13
- -1 aromatic dicarboxylic acid compound Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- 238000004804 winding Methods 0.000 claims abstract description 7
- 150000002429 hydrazines Chemical class 0.000 claims abstract description 6
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009998 heat setting Methods 0.000 claims abstract description 5
- 238000009966 trimming Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 15
- 230000002457 bidirectional effect Effects 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910000856 hastalloy Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011825 aerospace material Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical group O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
-
- 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
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The invention relates to an aromatic polyoxadiazole film and a preparation method thereof, comprising the following steps: aromatic dicarboxylic acid compound and hydrazine salt are used as monomers, and polycondensation reaction is carried out in fuming sulfuric acid to obtain aromatic polyoxadiazole solution; extruding the aromatic polyoxadiazole solution through a clothes hanger type casting die, and then conveying the extruded aromatic polyoxadiazole solution into a dilute sulfuric acid coagulation bath for coagulation forming to obtain a coagulated acid-containing wet state primary casting film; washing the acid-containing wet primary casting film to obtain a sulfuric acid-free primary casting film; and tensioning and drying the primary casting film without sulfuric acid, performing heat setting treatment at 200-350 ℃, and performing trimming and winding to obtain the aromatic polyoxadiazole film. The aromatic polyoxadiazole film can be widely used as a high-temperature resistant electric insulation film, a high-temperature resistant insulation paper/film composite material, a copper-coated film, a high-temperature resistant permeable film, a carbon film substrate, an aerospace material and the like.
Description
Technical Field
The invention relates to the technical field of film preparation, in particular to an aromatic polyoxadiazole film and a preparation method thereof.
Background
Aromatic Polyoxadiazole (POD) is an aromatic heterocyclic polymer material with good electric insulation, heat resistance, oxidation resistance, and the like, is insoluble in common organic solvents and most inorganic solvents, and is only decomposed and not melted at high temperature, so that the aromatic polyoxadiazole has wide application prospect in the fields of high temperature resistance, electric insulation, and the like. However, since the synthesis conditions are severe, the fluidity is poor, and the processability is poor, the synthesis of the POD polymer, and the molding and processing of materials such as films and fibers are relatively less developed, and particularly the molding and processing of films are more rare.
In the 60 s of the 20 th century, the U.S. scientists have first initiated studies on the preparation, structure and properties of aromatic polyoxadiazoles, after which POD polymers have received much attention for their good properties. The preparation of POD generally adopts a two-step method, namely, polyhydrazide is synthesized first, and then the POD material is obtained through high-temperature dehydration cyclization after processing and molding. The method has the advantages of complex technical route, high raw material cost, multiple material structure defects and poor mechanical property. At present, the two-step method is mainly limited to laboratory researches for preparing photoelectric materials and the like, but the literature about preparing high-temperature-resistant and functional films by using POD is not reported.
Disclosure of Invention
Based on this, it is necessary to provide a method for producing an aromatic polyoxadiazole film having better properties.
The preparation method of the aromatic polyoxadiazole film comprises the following steps:
aromatic dicarboxylic acid compound and hydrazine salt are used as monomers, and polycondensation reaction is carried out in fuming sulfuric acid to obtain aromatic polyoxadiazole solution;
extruding the aromatic polyoxadiazole solution through a clothes hanger type casting die, and then conveying the extruded aromatic polyoxadiazole solution into a dilute sulfuric acid coagulation bath for coagulation forming to obtain a coagulated acid-containing wet state primary casting film; the clothes hanger type casting die extrusion process comprises the following steps: the aromatic polyoxadiazole solution is subjected to efficient vacuum defoamation, then is conveyed to a coarse filter for coarse filtration, is conveyed to a fine filter for fine filtration, is conveyed to a clothes hanger type die, and is extruded to a solidification carrier roller in a die slit to form a sheet polyoxadiazole solution;
washing the acid-containing wet primary casting film to obtain a sulfuric acid-free primary casting film;
and tensioning and drying the primary casting film without sulfuric acid, performing heat setting treatment at 200-350 ℃, and performing trimming and winding to obtain the aromatic polyoxadiazole film.
In one embodiment, the pore diameter of the filter screen of the coarse filter is 40-80 μm, the filtering pressure is less than or equal to 1.0MPa, the pore diameter of the filter screen of the fine filter is 30-50 μm, and the filtering pressure is less than or equal to 3.0MPa.
In one embodiment, the mass concentration of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 20-50%, and the temperature of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 20-60 ℃.
In one embodiment, the mass concentration of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 40-45%, and the temperature of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 40-50 ℃.
In one embodiment, the step of washing is preceded by the step of: and carrying out wet state hot bath plasticization on the acid-containing wet state primary casting film, and then carrying out unidirectional or bidirectional stretching.
In one embodiment, the unidirectional or bidirectional stretching process is as follows: and (3) carrying out 1.1-4 times of unidirectional stretching on the acid-wet-state-containing primary casting film in unidirectional stretching equipment or 1.1-3 times of bidirectional stretching in bidirectional stretching equipment, wherein the stretching temperature is 40-50 ℃.
In one embodiment, the roughness of the inner surface of the runner of the hanger die is Ra.ltoreq.0.8 μm.
In one embodiment, the hanger die is 904 stainless steel, 904L stainless steel, hastelloy B-2 or hastelloy C-276.
In one embodiment, the inner surface of the runner of the hanger die is subjected to fine grinding or is plated with a platinum layer or a yellow platinum layer, and the thickness of the plating layer is 20-100 mu m.
The invention also provides an aromatic polyoxadiazole film which is prepared by the preparation method.
The invention utilizes the POD polymer solution to be easily solidified and molded in the dilute sulfuric acid solution, has the tensile property (more than 3 times of tensile property) which is incomparable with the solidification process of polyimide, aromatic polyamide and the like, and can process the POD into a high-temperature resistant, electric insulating and functional film with the thickness of tens of micrometers to hundreds of micrometers through the technical route of POD polymerization, casting, solidification molding, washing, drying and shaping and winding molding, and the mechanical, high-temperature resistant, electric insulating and other properties of the POD are comparable with those of polyimide films (such as Kapton), but the POD has good price advantage. The preparation method of the invention uses the production technology of viscose cellophane to fully utilize the characteristics of easy uniform solidification and forming and high-power stretching of the POD, and can achieve the expected purpose through high-temperature shaping. The thickness of the prepared film is 20-1000 mu m, the tensile strength is 50-400 MPa, the elongation at break is 20-80%, the initial decomposition temperature is more than 480 ℃, and the electrical breakdown strength is 100-300 kV. The film can be widely used as high temperature resistant electric insulation film, high temperature resistant insulation paper/film composite material, copper-clad film, high temperature resistant permeable film, carbon film base material, aerospace material and the like.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The preparation method of the aromatic polyoxadiazole film in one embodiment of the invention comprises the following steps S1 to S4:
s1, carrying out polycondensation reaction in fuming sulfuric acid by taking an aromatic dicarboxylic acid compound and hydrazine salt as monomers to obtain an aromatic polyoxadiazole solution.
S2, extruding the aromatic polyoxadiazole solution through a clothes hanger type casting die, and then conveying the extruded aromatic polyoxadiazole solution into a dilute sulfuric acid coagulating bath for coagulating and forming to obtain a coagulated acid-containing wet primary casting film. The extrusion process of the clothes rack type casting die comprises the following steps: the aromatic polyoxadiazole solution is subjected to high-efficiency vacuum defoamation, then is conveyed to a coarse filter for coarse filtration, is conveyed to a fine filter for fine filtration, is conveyed to a clothes hanger type die, and is extruded to a solidification carrier roller in a die slit to form the sheet polyoxadiazole solution.
S3, washing the acid-containing wet primary casting film to obtain the sulfuric acid-free primary casting film.
S4, tensioning and drying the primary casting film without sulfuric acid, performing heat setting treatment at 200-350 ℃, and performing trimming and winding to obtain the aromatic polyoxadiazole film.
The invention utilizes the POD polymer solution to be easily solidified and molded in the dilute sulfuric acid solution, has the tensile property (more than 3 times of tensile property) which is incomparable with the solidification process of polyimide, aromatic polyamide and the like, and can process the POD into a high-temperature resistant, electric insulating and functional film with the thickness of tens of micrometers to hundreds of micrometers through the technical route of POD polymerization, casting, solidification molding, washing, drying and shaping and winding molding, and the mechanical, high-temperature resistant, electric insulating and other properties of the POD are comparable with those of polyimide films (such as Kapton), but the POD has good price advantage. The preparation method of the invention uses the production technology of viscose cellophane to fully utilize the characteristics of easy uniform solidification and forming and high-power stretching of the POD, and can achieve the expected purpose through high-temperature shaping. The thickness of the prepared film is 20-1000 mu m, the tensile strength is 50-400 MPa, the elongation at break is 20-80%, the initial decomposition temperature is more than 480 ℃, and the electrical breakdown strength is 100-300 kV. The film can be widely used as high temperature resistant electric insulation film, high temperature resistant insulation paper/film composite material, copper-clad film, high temperature resistant permeable film, carbon film base material, aerospace material and the like.
In a specific example, the filter screen aperture of the coarse filter is 40-80 μm, the filter pressure is less than or equal to 1.0MPa, the filter screen aperture of the fine filter is 30-50 μm, and the filter pressure is less than or equal to 3.0MPa. Preferably, the material of the coarse filter and the fine filter is 316L stainless steel (standard grade 022Cr17Ni12Mo 2).
In a specific example, the mass concentration of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 20-50%, and the temperature of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 20-60 ℃. Preferably, the mass concentration of the dilute sulfuric acid in the dilute sulfuric acid coagulating bath is 40-45%, and the temperature of the dilute sulfuric acid in the dilute sulfuric acid coagulating bath is 40-50 ℃.
In a specific example, the step of washing is preceded by the step of: and (3) carrying out wet state hot bath plasticization on the acid-containing wet state primary casting film, and then carrying out unidirectional or bidirectional stretching. Specifically, the unidirectional or bidirectional stretching process comprises the following steps: the acid-wet-state-containing primary casting film is subjected to 1.1-4 times of unidirectional stretching in unidirectional stretching equipment or 1.1-3 times of bidirectional stretching in bidirectional stretching equipment, and the stretching temperature is 40-50 ℃.
In one specific example, the roughness of the inner surface of the runner of the hanger die is Ra 0.8 μm or less, i.e., a dark gloss surface and above accuracy is achieved, the surface finish is 10 or more, preferably the surface finish is 14 or more, i.e., a mirror finish is achieved.
In one specific example, the hanger die is made of 904 stainless steel (standard grade 0Cr20Ni25Mo5Cu 2), 904L stainless steel (standard grade 00Cr20Ni25Mo5Cu 2), hastelloy B-2 or hastelloy C-276.
In a specific example, the inner surface of the runner of the hanger die is subjected to finish grinding or is plated with a platinum layer or a yellow platinum layer, and the plating thickness is 20 μm to 100 μm. Preferably, the die-opening spacing of the hanger die is adjustable between 0.2 and 0.6mm, the processing temperature of the hanger die is adjustable between 30 and 120 ℃, and the preferred processing temperature is between 70 and 90 ℃.
In a specific example, the material of the solidified idler is 904 stainless steel (standard mark is 0Cr20Ni25Mo5Cu 2), 904L stainless steel (standard mark is 00Cr20Ni25Mo5Cu 2) or Polytetrafluoroethylene (PTFE), the outer surface of the solidified idler can be plated with platinum or yellow platinum, the thickness of the plating layer is 20-100 mu m, and the surface roughness of the surface of the plating layer reaches the precision of dark gloss surface and above, namely Ra is less than or equal to 0.8 mu m (the surface finish is more than or equal to 10). Preferably, the surface roughness reaches an accuracy of invisible marks and above, i.e., ra.ltoreq.1.6 μm (surface finish is 9 or more). Preferably, the diameter of the solidification carrier roller is 400-1000 mm, and the solidification carrier roller can circulate heat preservation water to enable the temperature of the roller surface to be 30-60 ℃.
In a specific example, the aromatic dicarboxylic acid compound contains one or more of the following groups, specifically, for example, terephthalic acid and the like.
In a specific example, the molar ratio of fuming sulfuric acid, aromatic dicarboxylic acid compound and hydrazine salt is (3-6) 1.0 (1.03-1.1). Preferably, the aromatic dicarboxylic acid compound comprises at least two types, wherein one type of the aromatic dicarboxylic acid compound is terephthalic acid, and the molar ratio of the terephthalic acid to other aromatic dicarboxylic acids is (0.50-1.00): 0.1-0.5. It will be appreciated that the number of moles of oleum is calculated as SO contained in oleum 3 Mole number of SO 3 The mass percentage of the (B) is 20% -40%. Preferably, the hydrazine salt is hydrazine sulfate.
In one specific example, the polycondensation reaction is performed in a three-stage process:
1) The reaction temperature in the first stage is 80-120 ℃ and the reaction time is 2-5 h;
2) The reaction temperature of the second stage is 110-140 ℃, the reaction time is 1-5 h, and a chain terminator is added when the second stage is finished;
3) The reaction temperature in the third stage is 130-160 ℃, and the reaction time is 0.5-3 h.
Preferably, the chain terminator is benzoic acid, and the addition amount of the chain terminator is 0.5% -3% of the mole number of the aromatic dicarboxylic acid in the reaction system of the polycondensation reaction.
The following are specific examples.
Example 1
Fuming sulfuric acid, terephthalic acid and hydrazine sulfate are mixed according to a molar ratio of 4:1:1 to carry out polycondensation reaction. The reaction temperature in the first stage is 100 ℃, and the reaction time is 4 hours; the reaction temperature of the second stage is 120-140 ℃, the reaction time is 3h, and a chain terminator is added when the second stage is finished; the reaction temperature in the third stage is 150 ℃ and the reaction time is 2 hours, so that the aromatic polyoxadiazole solution is obtained.
The method comprises the steps of carrying out high-efficiency vacuum defoamation on an aromatic polyoxadiazole solution, conveying the aromatic polyoxadiazole solution to a coarse filter for coarse filtration by a screw conveying pump, conveying the aromatic polyoxadiazole solution to a secondary fine filter for fine filtration by the screw conveying pump, accurately metering the aromatic polyoxadiazole solution by a gear metering pump, conveying the aromatic polyoxadiazole solution to a clothes hanger type die, and extruding the aromatic polyoxadiazole solution to a solidification carrier roller in a die slit to form the sheet polyoxadiazole solution. The aperture of a filter screen of the coarse filter is 80 mu m, and the filtering pressure is less than or equal to 1.0MPa; the pore diameter of the filter screen of the secondary fine filter is 50 mu m, the filtering pressure is less than or equal to 3.0Mpa, and the filter comprises a filter core and 316L stainless steel as the filter screen material. The clothes rack type mold is made of 904L stainless steel, the inner surface of a runner of the clothes rack type mold is plated with a platinum layer, and the thickness of the plating layer is 100 mu m. The surface roughness of the inner surface of the runner reaches the precision of dark gloss surface and above, namely Ra is less than or equal to 0.8 mu m (the surface finish is more than or equal to 10).
And conveying the sheet-shaped polyoxadiazole solution into a dilute sulfuric acid coagulation bath for coagulation forming to form the acid-containing wet state primary casting film. The coagulation bath adopts a dilute sulfuric acid aqueous solution, the concentration of the dilute sulfuric acid is 40 percent, and the temperature of the dilute sulfuric acid is 50 ℃.
Washing the nascent casting film containing acid wet state to obtain the nascent casting film without sulfuric acid. And tensioning and drying the primary casting film without sulfuric acid, performing heat setting treatment at 200-350 ℃, and performing trimming and winding to obtain the aromatic polyoxadiazole film.
The tensile strength of the aromatic polyoxadiazole film is 180MPa, the elongation at break is 80%, the initial decomposition temperature is more than 480 ℃, and the electrical breakdown strength is 170kV.
Comparative example 1
The present comparative example is different from example 1 in that the aromatic polyoxadiazole solution was directly extruded to the setting roller in the slit of the hanger die to form a sheet-like polyoxadiazole solution without the above-mentioned operations such as defoaming filtration.
The tensile strength of the obtained aromatic polyoxadiazole film is 90MPa, the elongation at break is 43%, the initial decomposition temperature is more than 480 ℃, and the electrical breakdown strength is 90kV.
Example 2
This example is substantially the same as example 1, except that the concentration of the dilute sulfuric acid is 20%, and the temperature of the dilute sulfuric acid is 30 ℃.
The tensile strength of the obtained aromatic polyoxadiazole film is 110MPa, the elongation at break is 58%, the initial decomposition temperature is more than 480 ℃, and the electrical breakdown strength is 120kV.
Example 3
This example is substantially the same as example 1 except that the filter mesh size of the coarse filter is 100. Mu.m, and the filter mesh size of the fine filter is 80. Mu.m.
The tensile strength of the obtained aromatic polyoxadiazole film is 140MPa, the elongation at break is 72%, the initial decomposition temperature is more than 480 ℃, and the electrical breakdown strength is 120kV.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The preparation method of the aromatic polyoxadiazole film is characterized by comprising the following steps of:
aromatic dicarboxylic acid compound and hydrazine salt are used as monomers, and polycondensation reaction is carried out in fuming sulfuric acid to obtain aromatic polyoxadiazole solution;
extruding the aromatic polyoxadiazole solution through a clothes hanger type casting die, and then conveying the extruded aromatic polyoxadiazole solution into a dilute sulfuric acid coagulation bath for coagulation forming to obtain a coagulated acid-containing wet state primary casting film; the clothes hanger type casting die extrusion process comprises the following steps: the aromatic polyoxadiazole solution is subjected to efficient vacuum defoamation, then is conveyed to a coarse filter for coarse filtration, is conveyed to a fine filter for fine filtration, is conveyed to a clothes hanger type die, and is extruded to a solidification carrier roller in a die slit to form a sheet polyoxadiazole solution; the pore diameter of the filter screen of the coarse filter is 40-80 mu m, the filtering pressure is less than or equal to 1.0MPa, the pore diameter of the filter screen of the fine filter is 30-50 mu m, and the filtering pressure is less than or equal to 3.0MPa;
washing the acid-containing wet primary casting film to obtain a sulfuric acid-free primary casting film;
and tensioning and drying the primary casting film without sulfuric acid, performing heat setting treatment at 200-350 ℃, and performing trimming and winding to obtain the aromatic polyoxadiazole film.
2. The method according to claim 1, wherein the mass concentration of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 20 to 50%, and the temperature of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 20 to 60 ℃.
3. The preparation method according to claim 2, wherein the mass concentration of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 40-45%, and the temperature of the dilute sulfuric acid in the dilute sulfuric acid coagulation bath is 40-50 ℃.
4. The method of claim 1, further comprising the step of, prior to the step of washing: and carrying out wet state hot bath plasticization on the acid-containing wet state primary casting film, and then carrying out unidirectional or bidirectional stretching.
5. The method according to claim 4, wherein the unidirectional or bidirectional stretching process is as follows: and (3) carrying out 1.1-4 times of unidirectional stretching on the acid-wet-state-containing primary casting film in unidirectional stretching equipment or 1.1-3 times of bidirectional stretching in bidirectional stretching equipment, wherein the stretching temperature is 40-50 ℃.
6. The method of claim 1, wherein the roughness of the inner surface of the runner of the hanger die is Ra 0.8 μm or less.
7. The method of claim 1, wherein the hanger die is 904 stainless steel, 904L stainless steel, hastelloy B-2 or hastelloy C-276.
8. The method according to claim 7, wherein the inner surface of the runner of the hanger die is subjected to fine grinding or is coated with a platinum layer or a platinum layer, and the thickness of the coating is 20 μm to 100 μm.
9. An aromatic polyoxadiazole film prepared by the preparation method according to any one of claims 1 to 8.
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| CN103934938A (en) * | 2014-04-17 | 2014-07-23 | 常州纺织服装职业技术学院 | Process of drying and shaping aromatic poly-1,3,4-oxadiazole casting film |
| CN103978707A (en) * | 2014-04-17 | 2014-08-13 | 常州纺织服装职业技术学院 | Washing technology of 1,3,4-oxadiazole acid-containing wet casting film |
| CN105418920A (en) * | 2015-12-28 | 2016-03-23 | 中国久远高新技术装备公司 | Aromatic polyoxadiazole and preparation method thereof, high-strength high-modulus flame-retardation aromatic polyoxadiazole fibers and preparation method thereof |
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| CN103934938A (en) * | 2014-04-17 | 2014-07-23 | 常州纺织服装职业技术学院 | Process of drying and shaping aromatic poly-1,3,4-oxadiazole casting film |
| CN103978707A (en) * | 2014-04-17 | 2014-08-13 | 常州纺织服装职业技术学院 | Washing technology of 1,3,4-oxadiazole acid-containing wet casting film |
| CN105418920A (en) * | 2015-12-28 | 2016-03-23 | 中国久远高新技术装备公司 | Aromatic polyoxadiazole and preparation method thereof, high-strength high-modulus flame-retardation aromatic polyoxadiazole fibers and preparation method thereof |
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