CN112979947A - Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film - Google Patents
Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film Download PDFInfo
- Publication number
- CN112979947A CN112979947A CN202110519809.5A CN202110519809A CN112979947A CN 112979947 A CN112979947 A CN 112979947A CN 202110519809 A CN202110519809 A CN 202110519809A CN 112979947 A CN112979947 A CN 112979947A
- Authority
- CN
- China
- Prior art keywords
- acid
- aromatic polyoxadiazole
- sulfuric acid
- stage
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 78
- 230000015271 coagulation Effects 0.000 claims description 54
- 238000005345 coagulation Methods 0.000 claims description 54
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 21
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims description 21
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 150000002429 hydrazines Chemical class 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 16
- YUWKPDBHJFNMAD-UHFFFAOYSA-N 2-fluoroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(F)=C1 YUWKPDBHJFNMAD-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 12
- AUIOTTUHAZONIC-UHFFFAOYSA-N 5-fluorobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(F)=CC(C(O)=O)=C1 AUIOTTUHAZONIC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000012493 hydrazine sulfate Substances 0.000 claims description 12
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 abstract description 50
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 72
- 239000000243 solution Substances 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical group [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 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
Landscapes
- 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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to aromatic polyoxadiazole, an aromatic polyoxadiazole film and a preparation method of the film, wherein the aromatic polyoxadiazole comprises a repeating unit A and a repeating unit B, and the structure of the repeating unit A is shown as a formula I:
i, performing primary filtration; the structure of the repeating unit B is at least one of a formula II, a formula III and a formula IV:
Ⅱ
Ⅲ
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an aromatic polyoxadiazole film, an aromatic polyoxadiazole film and a preparation method of the film.
Background
Aromatic polyoxadiazole is a high-performance polymer containing a benzene ring and an oxadiazole ring in a molecular chain, and is applied to various fields such as a high-temperature resistant field and an electric insulation protection field due to good high-temperature resistance stability, chemical resistance and electric insulation. However, its application in the field of optoelectronics is severely limited by its darker color and lower light transmittance.
In the prior art, the flame retardance of the aromatic polyoxadiazole is improved, and few reports on the optical performance of the aromatic polyoxadiazole are reported, so that the aromatic polyoxadiazole can be better applied to various fields, and the research and the preparation of the aromatic polyoxadiazole material with high light transmittance are necessary.
Disclosure of Invention
In view of the above-mentioned disadvantages in the prior art, an object of the present invention is to provide an aromatic polyoxadiazole, an aromatic polyoxadiazole thin film having a high light transmittance, in which the light transmittance exceeds 85% and the maximum light transmittance reaches 94% in a wavelength range of 400nm to 800nm, and a method for producing the thin film.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an aromatic polyoxadiazole, which comprises a repeating unit a and a repeating unit B, wherein the structure of the repeating unit a is shown in formula I:
Ⅰ；
the structure of the repeating unit B is at least one of a formula II, a formula III and a formula IV:
Ⅱ；
Ⅲ；
Ⅳ；
r is one of first main group metal elements;
the aromatic polyoxadiazole is obtained by performing polycondensation reaction on terephthalic acid, phthalic acid derivatives and hydrazine salt serving as reaction raw materials in fuming sulfuric acid, wherein the phthalic acid derivatives are at least one of 2-fluoroterephthalic acid, 5-fluoroisophthalic acid and isophthalic acid-5-sulfonate, and the molar ratio of the fuming sulfuric acid to the terephthalic acid to the phthalic acid derivatives to the hydrazine salt is (4-7): (0.7-0.8): (0.2-0.3): (1-1.5) wherein the molar number of the fuming sulfuric acid is the SO contained in the fuming sulfuric acid3In moles of (a).
The invention provides the aromatic polyoxadiazole in which 2-fluoroterephthalic acid, 5-fluoroisophthalic acid or isophthalic acid-5-sulfonate monomer participates in copolymerization, and the light transmittance of the aromatic polyoxadiazole is remarkably improved.
In a second aspect, the present invention provides an aromatic polyoxadiazole film prepared from the aromatic polyoxadiazole of the first aspect.
The aromatic polyoxadiazole film has high light transmittance, wherein the light transmittance exceeds 85% and the maximum light transmittance reaches 94% in a wavelength range of 400nm to 800 nm.
In a third aspect, the present invention provides a method for preparing the aromatic polyoxadiazole film according to the second aspect, comprising the steps of:
s1, carrying out polycondensation reaction in fuming sulfuric acid by taking terephthalic acid, phthalic acid derivatives and hydrazine salt as reaction raw materials to obtain an aromatic polyoxadiazole solution, wherein the phthalic acid derivatives are at least one of 2-fluoroterephthalic acid, 5-fluoroisophthalic acid and isophthalic acid-5-sulfonate;
s2, extruding the aromatic polyoxadiazole solution through a coat hanger type die, and sequentially conveying the solution into a first-stage coagulation bath, a second-stage coagulation bath and a third-stage coagulation bath for coagulation forming to obtain a coagulated acid-containing wet primary casting film, wherein each stage of coagulation bath comprises sulfuric acid and water, the weight ratio of the sulfuric acid to the water in the first-stage coagulation bath is (30: 70) - (50: 50), the weight ratio of the sulfuric acid to the water in the second-stage coagulation bath is (20: 80) - (25: 75), and the weight ratio of the sulfuric acid to the water in the third-stage coagulation bath is (2: 98) - (8: 92);
s3, washing the acid-containing wet primary casting film to obtain a primary casting film without sulfuric acid;
s4, carrying out biaxial stretching on the sulfuric acid-free nascent casting film, carrying out heat setting treatment at 300-450 ℃, and carrying out edge cutting and winding to obtain the aromatic polyoxadiazole film.
Preferably, in step S1, the molar ratio of oleum, terephthalic acid, phthalic acid derivative and hydrazine salt is (4-7): (0.7-0.8): (0.2-0.3): (1-1.5) wherein the molar number of oleum is the SO contained in oleum3In moles of (a).
In any of the above schemes, preferably, the hydrazonium salt is hydrazine sulfate or hydrazine hydrochloride, and the content of sulfur trioxide in the oleum is 20-40 wt%.
In any of the above embodiments, preferably, the polycondensation reaction is carried out in three stages:
the first stage is as follows: the reaction temperature is 90-130 ℃, and the reaction time is 3-5 h;
and a second stage: the reaction temperature is 140-170 ℃, the reaction time is 2-6 h, and a chain terminator is added when the second stage is finished;
and a third stage: the reaction temperature is 150-180 ℃, and the reaction time is 3-6 h.
In any of the above embodiments, preferably, the chain terminator is benzoic acid, and the addition amount of the chain terminator is 0.5% to 2% of the molar number of the hydrazine salt in the reaction system of the polycondensation reaction.
In any of the above schemes, preferably, the extrusion process of the coat hanger type die comprises: and (2) defoaming the aromatic polyoxadiazole solution, conveying the aromatic polyoxadiazole solution to a coarse filter for coarse filtration, conveying the aromatic polyoxadiazole solution to a fine filter for fine filtration, conveying the aromatic polyoxadiazole solution to a coat hanger type mold, and extruding the aromatic polyoxadiazole solution in a slit of the mold onto a solidification carrier roller to form the sheet polyoxadiazole solution.
In any of the above schemes, preferably, the aperture of the filter screen of the coarse filter is 50 μm to 70 μm, the filter pressure is less than or equal to 1.0MPa, the aperture of the filter screen of the fine filter is 40 μm to 50 μm, and the filter pressure is less than or equal to 2.0 MPa.
In any of the above embodiments, in step S2, the weight ratio of sulfuric acid to water in the first coagulation bath is (38: 62) - (42: 58), the weight ratio of sulfuric acid to water in the second coagulation bath is (22: 78) - (24: 76), and the weight ratio of sulfuric acid to water in the third coagulation bath is (4: 96) - (6: 94).
In any of the above embodiments, in step S2, the reaction temperature of the aromatic polyoxadiazole solution in each stage of the coagulation bath is preferably 40 to 70 ℃, and the reaction time is preferably 3 to 10 minutes.
Preferably in any of the above embodiments, the washing the acid-containing wet as-cast film comprises the steps of:
after primary water washing, alkaline washing and secondary water washing are carried out on the acid-containing wet primary casting film, the sulfuric acid-free primary casting film is obtained;
the alkaline washing adopts 1-5% of sodium hydroxide or sodium bicarbonate aqueous solution by mass fraction; the time of the first-stage water washing and the second-stage water washing is 5-20 minutes, and the temperature is 40-70 ℃; the alkaline washing time is 5-20 minutes, and the temperature is 40-70 ℃.
In any of the above schemes, preferably, in step S4, the biaxial stretching process is: and (3) carrying out 1-3 times of biaxial stretching on the sulfuric acid-free nascent casting film in biaxial stretching equipment, wherein the stretching temperature is 100-150 ℃.
In any of the above embodiments, preferably, in step S2, the aromatic polyoxadiazole solution is completely molded on a molding roll made of glass, ceramic, hastelloy or 904L stainless steel, and the molding roll has a surface roughness Ra < 0.4.
In any of the above embodiments, the aromatic polyoxadiazole solution preferably has a residence time of 10 to 90 seconds on the forming roll.
In any of the above schemes, preferably, each stage of the coagulation bath further includes sulfate, and the addition amount of the sulfate is 0.2% -20% of the mole number of the sulfuric acid in each stage of the coagulation bath.
In any of the above embodiments, preferably, the sulfate is at least one of sodium sulfate and potassium sulfate.
In any of the above aspects, it is preferable that the method further comprises, before the winding, the steps of:
tempering treatment is carried out at 250-300 ℃.
The preparation method provided by the invention has the advantages of simple steps, convenience in operation and control, stable quality, high production efficiency and low production cost, and can be used for large-scale industrial production.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments, equipment and the like used in the following examples are either commercially available or available by existing methods; the dosage of the reagent is the dosage of the reagent in the conventional experiment operation if no special description exists; the experimental methods are conventional methods unless otherwise specified.
In a first aspect, embodiments of the present invention provide an aromatic polyoxadiazole comprising a repeating unit a and a repeating unit B, wherein the structure of the repeating unit a is shown in formula I:
Ⅰ；
the structure of the repeating unit B is at least one of a formula II, a formula III and a formula IV:
Ⅱ；
Ⅲ；
Ⅳ；
r is one of first main group metal elements;
the aromatic polyoxadiazole is obtained by performing polycondensation reaction on terephthalic acid, phthalic acid derivatives and hydrazine salt serving as reaction raw materials in fuming sulfuric acid, wherein the phthalic acid derivatives are at least one of 2-fluoroterephthalic acid, 5-fluoroisophthalic acid and isophthalic acid-5-sulfonate, and the molar ratio of the fuming sulfuric acid to the terephthalic acid to the phthalic acid derivatives to the hydrazine salt is (4-7): (0.7-0.8): (0.2-0.3): (1-1.5) wherein the molar number of the fuming sulfuric acid is the SO contained in the fuming sulfuric acid3In moles of (a).
R is one of the first main group metal elements, and for example, R may be lithium, sodium, potassium or the like.
The embodiment of the invention provides the aromatic polyoxadiazole in which the 2-fluoroterephthalic acid, 5-fluoroisophthalic acid or isophthalic acid-5-sulfonate monomer participates in copolymerization, and the light transmittance of the aromatic polyoxadiazole is obviously improved.
In a second aspect, embodiments of the present invention provide an aromatic polyoxadiazole film prepared from the aromatic polyoxadiazole of the first aspect.
The aromatic polyoxadiazole film can be applied to the fields of photoelectricity, covering films, fuel cell pile proton exchange membranes, chip bearing films, high-temperature adhesive tape substrates, TFT substrates, flexible display substrates, LED lamp strip substrates, FPC substrates, graphite heat dissipation film substrates, lithium battery diaphragms and aerospace military industry.
The aromatic polyoxadiazole film has high light transmittance, wherein the light transmittance exceeds 85% and the maximum light transmittance reaches 94% in a wavelength range of 400nm to 800 nm.
In a third aspect, embodiments of the present invention provide a method for preparing an aromatic polyoxadiazole film as described in the second aspect, the method comprising the steps of:
s1, carrying out polycondensation reaction in fuming sulfuric acid by taking terephthalic acid, phthalic acid derivatives and hydrazine salt as reaction raw materials to obtain an aromatic polyoxadiazole solution, wherein the phthalic acid derivatives are at least one of 2-fluoroterephthalic acid, 5-fluoroisophthalic acid and isophthalic acid-5-sulfonate;
s2, extruding the aromatic polyoxadiazole solution through a coat hanger type die, and sequentially conveying the solution into a first-stage coagulation bath, a second-stage coagulation bath and a third-stage coagulation bath for coagulation forming to obtain a coagulated acid-containing wet primary casting film, wherein each stage of coagulation bath comprises sulfuric acid and water, the weight ratio of the sulfuric acid to the water in the first-stage coagulation bath is (30: 70) - (50: 50), the weight ratio of the sulfuric acid to the water in the second-stage coagulation bath is (20: 80) - (25: 75), and the weight ratio of the sulfuric acid to the water in the third-stage coagulation bath is (2: 98) - (8: 92);
s3, washing the acid-containing wet primary casting film to obtain a primary casting film without sulfuric acid;
s4, carrying out biaxial stretching on the sulfuric acid-free nascent casting film, carrying out heat setting treatment at 300-450 ℃, and carrying out edge cutting and winding to obtain the aromatic polyoxadiazole film.
The aromatic polyoxadiazole may be prepared by step S1.
According to the embodiment of the invention, the number of stages of the coagulating bath and the component concentration are selected, so that the concentration difference between sulfuric acid in the film and sulfuric acid in the coagulating bath is reduced, the impact of the sulfuric acid precipitation process on the film is weakened, the precipitation time of the sulfuric acid is prolonged, the sulfuric acid in the film is more thoroughly precipitated, and the prepared film not only has excellent mechanical properties, but also has high light transmittance.
The thickness of the film prepared by the preparation method provided by the embodiment of the invention is 5-800 μm.
The preparation method provided by the embodiment of the invention has the advantages of simple steps, convenient operation and control, stable quality, high production efficiency and low production cost, and can be used for large-scale industrial production.
The structure of the 2-fluoroterephthalic acid is shown as the formula V:
Ⅴ。
the structure of the 5-fluoroisophthalic acid is shown as a formula VI:
Ⅵ。
the isophthalic acid-5-sulfonate can be isophthalic acid-5-sodium sulfonate, and the structure of the isophthalic acid-5-sodium sulfonate is shown as a formula VII:
Ⅶ。
further, in step S1, the molar ratio of oleum, terephthalic acid, phthalic acid derivative and hydrazine salt is (4-7): (0.7-0.8): (0.2-0.3): (1-1.5) wherein the molar number of oleum is the SO contained in oleum3If the amount of the phthalic acid derivative is too large, the mechanical properties of the resulting film are significantly reduced, and if the amount of the phthalic acid derivative is too small, the light transmittance of the film cannot be significantly improved. Such as aThe molar ratio of the fuming sulfuric acid, the terephthalic acid, the phthalic acid derivative and the hydrazine salt can be 4:0.7:0.3:1.1, 5:0.8:0.2:1.2, 7:0.8:0.2:1.4 and the like.
Further, the hydrazonium salt is hydrazine sulfate or hydrazine hydrochloride, and the content of sulfur trioxide in the oleum is 20-40 wt%, for example, the content can be 20wt%, 30wt% or 40 wt%.
Further, the polycondensation reaction is carried out in three stages:
the first stage is as follows: the reaction temperature is 90-130 ℃ (for example, the reaction temperature can be 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃) and the reaction time is 3-5 h (for example, the reaction time can be 3h, 4h or 5 h);
and a second stage: the reaction temperature is 140-170 ℃ (for example, the reaction temperature can be 140 ℃, 150 ℃ or 170 ℃, etc.), the reaction time is 2-6 h (for example, the reaction time can be 3h, 4h or 5h, etc.), and a chain terminator is added when the second stage is finished;
and a third stage: the reaction temperature is 150-180 ℃ (for example, the reaction temperature can be 150 ℃, 170 ℃ or 180 ℃) and the reaction time is 3-6 h (for example, the reaction time can be 3h, 4h or 5 h).
The first stage is prepolymerization, the second stage is polymerization, and the third stage is cyclization.
Further, the chain terminator is benzoic acid, and the addition amount of the chain terminator is 0.5% to 2% of the mole number of the hydrazine salt in the reaction system of the polycondensation reaction, for example, if the mole number of the hydrazine salt in the reaction system is 100mol, the addition amount of the chain terminator can be 0.5mol, 1mol, 1.5mol, 2mol, or the like.
Further, the extrusion process of the coat hanger type die comprises the following steps: and (2) defoaming the aromatic polyoxadiazole solution, conveying the aromatic polyoxadiazole solution to a coarse filter for coarse filtration, conveying the aromatic polyoxadiazole solution to a fine filter for fine filtration, conveying the aromatic polyoxadiazole solution to a coat hanger type mold, and extruding the aromatic polyoxadiazole solution in a slit of the mold onto a solidification carrier roller to form the sheet polyoxadiazole solution.
The pore size of the filter net of the coarse filter is 50-70 μm (for example, the pore size can be 50, 60 or 70 μm), the filtration pressure is less than or equal to 1.0MPa, the pore size of the filter net of the fine filter is 40-50 μm (for example, the pore size can be 40, 42, 44, 46 or 50 μm), and the filtration pressure is less than or equal to 2.0 MPa.
Further, in step S2, the weight ratio of sulfuric acid to water in the primary coagulation bath is (38: 62) - (42: 58), and for example, the weight ratio may be 38:62, 40:60, 42:58, or the like.
Further, in step S2, the weight ratio of sulfuric acid to water in the secondary coagulation bath is (22: 78) - (24: 76), and for example, the weight ratio may be 22:78, 23:77, 24:76, or the like.
Further, in step S2, the weight ratio of sulfuric acid to water in the third-stage coagulation bath is (4: 96) - (6: 94), and for example, the weight ratio may be 4:96, 5:95, or 6: 94.
Further, in step S2, the reaction temperature of the aromatic polyoxadiazole solution in each stage of the coagulation bath is 40 to 70 ℃, for example, the temperature may be 40 ℃, 50 ℃, 60 ℃ or 70 ℃, and the like, and as the temperature of the coagulation bath increases, the proportion of coarse crystals in the film crystals decreases, the proportion of fine crystals increases, the arrangement is more orderly, the light transmittance increases, but the mechanical properties decrease, and in order to ensure that the mechanical properties of the film are excellent and the transmittance is high, the temperature is preferably 45 to 50 ℃.
Further, in step S2, the reaction time of the aromatic polyoxadiazole solution in each stage of the coagulation bath is 3 to 10 minutes, for example, the reaction time may be 3 minutes, 5 minutes, 7 minutes, 10 minutes, or the like.
Further, the washing the acid-containing wet as-cast film comprises the following steps:
and after primary water washing, alkaline washing and secondary water washing of the acid-containing wet primary casting film, obtaining the sulfuric acid-free primary casting film.
Further, the alkaline washing adopts 1-5% of sodium hydroxide or sodium bicarbonate aqueous solution by mass, for example, the mass fraction can be 1%, 2%, 4% or 5%.
Furthermore, the time of the first stage water washing, the second stage water washing and the alkali washing is 5-20 minutes (for example, the time can be 5 minutes, 10 minutes, 15 minutes or 20 minutes) and the temperature is 40-70 ℃ (for example, the temperature can be 40 ℃, 50 ℃, 60 ℃ or 70 ℃ and the like).
Further, in step S4, the biaxial stretching process includes: the sulfuric acid-free nascent casting film is subjected to biaxial stretching by 1 to 3 times (for example, 1 time, 2 times, or 3 times) in a biaxial stretching device at a stretching temperature of 100 to 150 ℃ (for example, at a temperature of 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or 150 ℃).
Further, in step S2, the aromatic polyoxadiazole solution is completely molded on a molding roll made of glass, ceramic, hastelloy or 904L stainless steel, and the surface roughness Ra of the molding roll is less than 0.4.
Further, the residence time of the aromatic polyoxadiazole solution on the forming roll is 10-90 seconds, for example, the residence time may be 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds, and the like, and the residence time refers to the time from the beginning of the aromatic polyoxadiazole solution passing through each stage of the coagulation bath onto the forming roll to the end of the time when the film can be peeled off the forming roll without roll sticking residue.
Furthermore, each stage of the coagulation bath also comprises sulfate, the addition amount of the sulfate is 0.2-20% of the mole number of the sulfuric acid in each stage of the coagulation bath, for example, the addition amount of the sulfate is 0.2%, 2%, 5%, 10%, 15%, 20%, or the like, preferably 3-5% of the mole number of the sulfuric acid in the coagulation bath, and the sulfate is added into the coagulation bath, so that the film can be smoother and easier to be peeled from the forming roller.
Further, the sulfate is at least one of sodium sulfate and potassium sulfate.
Further, the method also comprises the following step of tempering at 250-300 ℃ before winding, and the tempering can relieve the stress of the edge film.
Further, in step S4, the heat setting treatment at 300-450 ℃ (for example, 300 ℃, 350 ℃, 400 ℃ or 450 ℃) is beneficial to improving the high temperature resistance of the film, reducing the Coefficient of Thermal Expansion (CTE), and improving the dimensional stability.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Fuming sulfuric acid: SO (SO)320 percent of fuming sulfuric acid.
Example 1
S1: fuming sulfuric acid, terephthalic acid, sodium 5-isophthalate and hydrazine sulfate are mixed according to a molar ratio of 5: 0.7:0.3: 1.2, mixing, and carrying out polycondensation reaction to obtain the aromatic polyoxadiazole solution.
The polycondensation reaction is carried out in three stages: the first stage is as follows: the reaction temperature is 100 ℃, and the reaction time is 4 hours; and a second stage: the reaction temperature is 145 ℃, the reaction time is 4 hours, and benzoic acid is added when the second stage is finished, wherein the adding amount of the benzoic acid is 1 percent of the mole number of the hydrazine sulfate in the reaction system of the polycondensation reaction; and a third stage: the reaction temperature is 170 ℃ and the reaction time is 5 h.
S2: and (2) defoaming the aromatic polyoxadiazole solution, conveying the aromatic polyoxadiazole solution to a coarse filter for coarse filtration, conveying the aromatic polyoxadiazole solution to a fine filter for fine filtration, accurately metering the aromatic polyoxadiazole solution by using a gear metering pump, conveying the aromatic polyoxadiazole solution to a clothes rack type mould, and extruding the aromatic polyoxadiazole solution in a slit of the mould onto a solidification carrier roller to form the sheet polyoxadiazole solution. The aperture of the filter screen of the coarse filter is 60 mu m, the filtering pressure is less than or equal to 1.0MPa, the aperture of the filter screen of the fine filter is 40 mu m, and the filtering pressure is less than or equal to 2.0 MPa.
And sequentially conveying the sheet polyoxadiazole solution to a first-stage coagulation bath (the reaction temperature is 45 ℃, and the reaction time is 4 minutes), a second-stage coagulation bath (the reaction temperature is 45 ℃, and the reaction time is 5 minutes) and a third-stage coagulation bath (the reaction temperature is 45 ℃, and the reaction time is 7 minutes) for coagulation forming to obtain a coagulated acid-containing wet primary cast film, wherein each stage of coagulation bath consists of sulfuric acid and water, the weight ratio of the sulfuric acid to the water in the first-stage coagulation bath is 40:60, the weight ratio of the sulfuric acid to the water in the second-stage coagulation bath is 23:77, and the weight ratio of the sulfuric acid to the water in the third-stage coagulation bath is 5: 95.
The aromatic polyoxadiazole solution is completely molded on a molding roller, the residence time is 40 seconds, and the molding roller is made of 904L stainless steel.
S3, subjecting the acid-containing wet primary casting film to primary water washing (at 45 ℃ for 10 minutes), alkaline washing (at 45 ℃ for 15 minutes) and secondary water washing (at 45 ℃ for 15 minutes) to obtain a primary casting film without sulfuric acid, wherein the alkaline washing is a sodium hydroxide aqueous solution with the mass fraction of 1%.
S4, biaxially stretching the sulfuric acid-free nascent casting film at 110 ℃ for 2 times in a biaxial stretching device, drying, controlling the water content of the film to be below 10%, then carrying out heat setting treatment at 400 ℃, cutting edges and winding to obtain the aromatic polyoxadiazole film.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limiting oxygen index of 40 percent, the tensile strength of 180MPa and the elongation at break of 80 percent, and has the light transmittance of over 90 percent, the maximum light transmittance of 94 percent and the light transmittance of 92 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
According to performance parameters, the film not only has good mechanical properties and flame retardant properties, but also has high light transmittance.
Example 2
Substantially the same as in step S1 in example 1, except that sodium 5-sulfoisophthalate was replaced with 2-fluoroterephthalic acid.
Is exactly the same as the steps S2 to S4 in the embodiment 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limited oxygen index of 34 percent, the tensile strength of 190MPa and the elongation at break of 82 percent, and has the light transmittance of over 85 percent, the maximum light transmittance of 89 percent and the light transmittance of 87 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
Example 3
Substantially the same as in step S1 in example 1, except that sodium 5-sulfoisophthalate was replaced with 5-fluoroisophthalic acid.
Is exactly the same as the steps S2 to S4 in the embodiment 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limited oxygen index of 36 percent, the tensile strength of 182MPa and the elongation at break of 81 percent, and has the light transmittance of more than 87 percent, the maximum light transmittance of 91 percent and the light transmittance of 89 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
Comparative example 1
Substantially the same as in step S1 in example 1, except that fuming sulfuric acid, terephthalic acid and hydrazine sulfate were mixed in a molar ratio of 5: 1: 1.2 mixing and carrying out polycondensation reaction.
Is exactly the same as the steps S2 to S4 in the embodiment 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limiting oxygen index of 21 percent, the tensile strength of 200MPa and the elongation at break of 85 percent, and has the light transmittance of over 60 percent, the maximum light transmittance of 65 percent and the light transmittance of 61 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
Comparative example 2
Exactly the same as step S1 in embodiment 1.
Substantially the same as step S2 in example 1, except that the polyoxadiazole solution in the form of sheet was fed only to the first-stage coagulation bath (reaction temperature 45 ℃ c., reaction time 15 minutes) in which the weight ratio of sulfuric acid to water was 40:60 for coagulation forming.
Identical to steps S3 and S4 in example 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limited oxygen index of 39%, the tensile strength of 150MPa and the elongation at break of 63%, and has the light transmittance of over 79%, the maximum light transmittance of 83% and the light transmittance of 81% at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
Comparative example 3
Exactly the same as step S1 in embodiment 1.
Substantially the same as in step S2 in example 1, except that the reaction temperature of each stage of the coagulation bath was 55 ℃.
Identical to steps S3 and S4 in example 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limiting oxygen index of 37 percent, the tensile strength of 150MPa and the elongation at break of 63 percent, and has the light transmittance of over 90 percent, the maximum light transmittance of 93 percent and the light transmittance of 91 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
As can be seen from the film performance parameters, compared with example 1, the light transmittance is not greatly different, and the mechanical properties are remarkably reduced.
Comparative example 4
Substantially the same as in step S1 of example 1, except that the molar ratio of fuming sulfuric acid, terephthalic acid, sodium 5-sulfoisophthalate and hydrazine sulfate was 5: 0.9: 0.1: 1.2.
is exactly the same as the steps S2 to S4 in the embodiment 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limiting oxygen index of 37 percent, the tensile strength of 185MPa and the elongation at break of 82 percent, and has the light transmittance of more than 76 percent, the maximum light transmittance of 81 percent and the light transmittance of 79 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
From the performance parameters, the light transmittance is obviously reduced by reducing the dosage of the m-phthalic acid-5-sodium sulfonate.
Similarly, if the molar ratio of oleum, terephthalic acid, 2-fluoroterephthalic acid and hydrazine sulfate is 5: 0.9: 0.1: 1.2 or the molar ratio of oleum, terephthalic acid, 5-fluoroisophthalic acid and hydrazine sulfate is 5: 0.9: 0.1: at 1.2, the light transmittance was also significantly reduced as compared with example 2 or example 3.
Comparative example 5
Substantially the same as in step S1 of example 1, except that the molar ratio of fuming sulfuric acid, terephthalic acid, sodium 5-sulfoisophthalate and hydrazine sulfate was 5: 0.5: 0.5: 1.2.
is exactly the same as the steps S2 to S4 in the embodiment 1.
The film performance parameters are as follows: the finished film has the thickness of 25 mu m, the limiting oxygen index of 42 percent, the tensile strength of 161MPa and the elongation at break of 68 percent, and has the light transmittance of over 90 percent, the maximum light transmittance of 93 percent and the light transmittance of 91 percent at the wavelength of 550nm within the wavelength range of 400nm to 800 nm.
According to the performance parameters, the light transmittance of the film is not obviously changed and the mechanical property is obviously reduced by increasing the using amount of the m-phthalic acid-5-sodium sulfonate.
Similarly, if the molar ratio of oleum, terephthalic acid, 2-fluoroterephthalic acid and hydrazine sulfate is 5: 0.5: 0.5: 1.2 or the molar ratio of oleum, terephthalic acid, 5-fluoroisophthalic acid and hydrazine sulfate is 5: 0.5: 0.5: 1.2, the light transmittance of the film was not significantly changed and the mechanical properties were significantly reduced, as compared with example 2 or example 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. An aromatic polyoxadiazole comprising a repeating unit A and a repeating unit B, wherein the repeating unit A has a structure represented by formula I:
Ⅰ；
the structure of the repeating unit B is at least one of a formula II, a formula III and a formula IV:
Ⅱ；
Ⅲ；
Ⅳ；
r is one of first main group metal elements;
the aromatic polyoxadiazole is obtained by performing polycondensation reaction on terephthalic acid, phthalic acid derivatives and hydrazine salt serving as reaction raw materials in fuming sulfuric acid, wherein the phthalic acid derivatives are at least one of 2-fluoroterephthalic acid, 5-fluoroisophthalic acid and isophthalic acid-5-sulfonate, and the molar ratio of the fuming sulfuric acid to the terephthalic acid to the phthalic acid derivatives to the hydrazine salt is (4-7): (0.7-0.8): (0.2-0.3): (1-1.5) wherein the molar number of the fuming sulfuric acid is the SO contained in the fuming sulfuric acid3In moles of (a).
2. An aromatic polyoxadiazole film which is produced from the aromatic polyoxadiazole of claim 1.
3. A method of producing the aromatic polyoxadiazole film of claim 2, comprising the steps of:
s1, carrying out polycondensation reaction in fuming sulfuric acid by taking terephthalic acid, phthalic acid derivatives and hydrazine salt as reaction raw materials to obtain an aromatic polyoxadiazole solution, wherein the phthalic acid derivatives are at least one of 2-fluoroterephthalic acid, 5-fluoroisophthalic acid and isophthalic acid-5-sulfonate;
s2, extruding the aromatic polyoxadiazole solution through a coat hanger type die, and sequentially conveying the solution into a first-stage coagulation bath, a second-stage coagulation bath and a third-stage coagulation bath for coagulation forming to obtain a coagulated acid-containing wet primary casting film, wherein each stage of coagulation bath comprises sulfuric acid and water, the weight ratio of the sulfuric acid to the water in the first-stage coagulation bath is (30: 70) - (50: 50), the weight ratio of the sulfuric acid to the water in the second-stage coagulation bath is (20: 80) - (25: 75), and the weight ratio of the sulfuric acid to the water in the third-stage coagulation bath is (2: 98) - (8: 92);
s3, washing the acid-containing wet primary casting film to obtain a primary casting film without sulfuric acid;
s4, carrying out biaxial stretching on the sulfuric acid-free nascent casting film, carrying out heat setting treatment at 300-450 ℃, and carrying out edge cutting and winding to obtain the aromatic polyoxadiazole film.
4. The method for producing an aromatic polyoxadiazole film according to claim 3, wherein in step S1:
the molar ratio of the fuming sulfuric acid to the terephthalic acid to the phthalic acid derivative to the hydrazine salt is (4-7): (0.7-0.8): (0.2-0.3): (1-1.5) wherein the molar number of the fuming sulfuric acid is the SO contained in the fuming sulfuric acid3In moles of (a).
5. The method for preparing an aromatic polyoxadiazole film according to claim 3, wherein the hydrazonium salt is hydrazine sulfate or hydrazine hydrochloride, and the content of sulfur trioxide in the oleum is 20-40 wt%.
6. The method for producing an aromatic polyoxadiazole film according to claim 3, wherein the polycondensation reaction is carried out in three stages:
the first stage is as follows: the reaction temperature is 90-130 ℃, and the reaction time is 3-5 h;
and a second stage: the reaction temperature is 140-170 ℃, the reaction time is 2-6 h, and a chain terminator is added when the second stage is finished;
and a third stage: the reaction temperature is 150-180 ℃, and the reaction time is 3-6 h.
7. The method for preparing an aromatic polyoxadiazole film according to claim 6, wherein the chain terminator is benzoic acid, and the amount of the chain terminator added is 0.5 to 2 mol% of the hydrazine salt in the reaction system of the polycondensation reaction.
8. The method for preparing the aromatic polyoxadiazole film according to claim 3, wherein the coat hanger type die extrusion process comprises: and (2) defoaming the aromatic polyoxadiazole solution, conveying the aromatic polyoxadiazole solution to a coarse filter for coarse filtration, conveying the aromatic polyoxadiazole solution to a fine filter for fine filtration, conveying the aromatic polyoxadiazole solution to a coat hanger type mold, and extruding the aromatic polyoxadiazole solution in a slit of the mold onto a solidification carrier roller to form the sheet polyoxadiazole solution.
9. The method of claim 8, wherein the coarse filter has a filter mesh size of 50 to 70 μm and a filter pressure of 1.0MPa or less, and the fine filter has a filter mesh size of 40 to 50 μm and a filter pressure of 2.0MPa or less.
10. The method of producing an aromatic polyoxadiazole film according to claim 3, wherein each stage of the coagulation bath further comprises a sulfate, and the sulfate is added in an amount of 0.2 to 20% by mole of the sulfate in each stage of the coagulation bath.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110519809.5A CN112979947B (en) | 2021-05-13 | 2021-05-13 | Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film |
| PCT/CN2022/092156 WO2022237827A1 (en) | 2021-05-13 | 2022-05-11 | Aromatic polyoxadiazole, and aromatic polyoxadiazole film and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110519809.5A CN112979947B (en) | 2021-05-13 | 2021-05-13 | Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112979947A true CN112979947A (en) | 2021-06-18 |
| CN112979947B CN112979947B (en) | 2021-08-20 |
Family
ID=76337671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110519809.5A Active CN112979947B (en) | 2021-05-13 | 2021-05-13 | Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112979947B (en) |
| WO (1) | WO2022237827A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022237827A1 (en) * | 2021-05-13 | 2022-11-17 | 陈瑾 | Aromatic polyoxadiazole, and aromatic polyoxadiazole film and preparation method therefor |
| CN118307777A (en) * | 2024-06-05 | 2024-07-09 | 陕西爱弗特智能装备科技有限公司 | Coating equipment for aromatic polyoxadiazole film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1407439A (en) * | 1971-11-26 | 1975-09-24 | Monsanto Co | Production of polymer solutions and of aromatic oxadiazole/ n-alkyl hydrazide copolymers therefrom |
| CN1704399A (en) * | 2004-05-28 | 2005-12-07 | 株式会社日本触媒 | Fluorine-containing compound |
| CN101235147A (en) * | 2007-01-31 | 2008-08-06 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Production of a functionalized polytriazole polymer |
| US20090312474A1 (en) * | 2008-06-12 | 2009-12-17 | General Electric Company | High temperature polymer composites and methods of making the same |
| CN102015820A (en) * | 2008-04-25 | 2011-04-13 | 住友化学株式会社 | Polymeric compound having residue of nitrogenated heterocyclic compound |
| US20120293749A1 (en) * | 2002-08-28 | 2012-11-22 | Sumitomo Chemical Company, Limited | Polymer compound and polymer light-emitting device using the same |
| CN103261274A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Sulfonated polyoxadiazole polymers articles |
| CN103261275A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Preparation of sulfonated polyoxadiazole polymers |
| CN109306180A (en) * | 2018-09-29 | 2019-02-05 | 王庭辉 | A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film |
| CN110194837A (en) * | 2019-06-27 | 2019-09-03 | 四川大学 | A kind of fire-retardant aromatic series polyoxadiazoles polymer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280380A (en) * | 2018-09-29 | 2019-01-29 | 刘文熙 | A kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant and preparation method thereof and application in fiber or film |
| CN111410740B (en) * | 2020-06-09 | 2020-12-08 | 李艺 | Preparation method of aromatic polyoxadiazole polymer fiber |
| CN112979947B (en) * | 2021-05-13 | 2021-08-20 | 陈瑾 | Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film |
-
2021
- 2021-05-13 CN CN202110519809.5A patent/CN112979947B/en active Active
-
2022
- 2022-05-11 WO PCT/CN2022/092156 patent/WO2022237827A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1407439A (en) * | 1971-11-26 | 1975-09-24 | Monsanto Co | Production of polymer solutions and of aromatic oxadiazole/ n-alkyl hydrazide copolymers therefrom |
| US20120293749A1 (en) * | 2002-08-28 | 2012-11-22 | Sumitomo Chemical Company, Limited | Polymer compound and polymer light-emitting device using the same |
| CN1704399A (en) * | 2004-05-28 | 2005-12-07 | 株式会社日本触媒 | Fluorine-containing compound |
| CN101235147A (en) * | 2007-01-31 | 2008-08-06 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Production of a functionalized polytriazole polymer |
| CN102015820A (en) * | 2008-04-25 | 2011-04-13 | 住友化学株式会社 | Polymeric compound having residue of nitrogenated heterocyclic compound |
| US20090312474A1 (en) * | 2008-06-12 | 2009-12-17 | General Electric Company | High temperature polymer composites and methods of making the same |
| CN103261274A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Sulfonated polyoxadiazole polymers articles |
| CN103261276A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Sulfonated polyoxadiazole polymers |
| CN103261275A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Preparation of sulfonated polyoxadiazole polymers |
| CN109306180A (en) * | 2018-09-29 | 2019-02-05 | 王庭辉 | A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film |
| CN110194837A (en) * | 2019-06-27 | 2019-09-03 | 四川大学 | A kind of fire-retardant aromatic series polyoxadiazoles polymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ALI HAYEK，等: "Unprecedented Sour Mixed-Gas Permeation Properties of Fluorinated Polyazole-Based Membranes", 《APPLIED POLYMER MATERIALS》 * |
| 李志愿，等: "湿法成型条件对聚芳噁二唑薄膜结构与性能的影响", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022237827A1 (en) * | 2021-05-13 | 2022-11-17 | 陈瑾 | Aromatic polyoxadiazole, and aromatic polyoxadiazole film and preparation method therefor |
| CN118307777A (en) * | 2024-06-05 | 2024-07-09 | 陕西爱弗特智能装备科技有限公司 | Coating equipment for aromatic polyoxadiazole film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112979947B (en) | 2021-08-20 |
| WO2022237827A1 (en) | 2022-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112979947B (en) | Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film | |
| US4075172A (en) | Novel aromatic copolyamides prepared from 3,4' diphenylene type diamines, and shaped articles therefrom | |
| US4606875A (en) | Process for preparing shaped articles of rigid rod heterocyclic liquid crystalline polymers | |
| WO1990014379A1 (en) | Poly(arylene ether ketone), method of its production, and its use | |
| CN110194837B (en) | Flame-retardant aromatic polyoxadiazole polymer and preparation method thereof | |
| JPH03205432A (en) | Polyimide film and its production | |
| WO2024036938A1 (en) | Heat-resistant and tensile-strength-enhanced polyester film, preparation method therefor and composite current collector | |
| CN1932091A (en) | Prepn process of polyimide fiber | |
| WO2021164143A1 (en) | Polyolefin porous membrane and preparation method therefor | |
| JP2014001363A (en) | Metal bonding biaxially oriented polyarylene sulfide film | |
| CN111516350B (en) | High-brightness mould pressing polyester film and preparation method thereof | |
| CN115873238B (en) | Meta-aramid polymer with grid structure and preparation method and application thereof | |
| CN110894291B (en) | Aromatic polyoxadiazole film and preparation method thereof | |
| CN111533980A (en) | Preparation method of stretch-resistant polyethylene film | |
| US4801416A (en) | Transparent and little colored polyarylenethioether primary melt molding, preparation and utilization thereof | |
| JPH11228695A (en) | Imide skeleton-containing ethylene naphthalate | |
| CN111087616A (en) | Method for preparing block type polyamic acid solution | |
| JP2936676B2 (en) | Heat resistant film | |
| CN115636965B (en) | High-transmittance polyisophthaloyl metaphenylene diamine film and preparation method thereof | |
| EP4294863A1 (en) | High hardness films | |
| CN118206739A (en) | Polyaryletherketone containing terminal phenolic hydroxyl groups, preparation method thereof and preparation method of polyaryletherketone film material | |
| JPH03217452A (en) | Heat-resistant film and stretched heat-resistant film | |
| JPH06184819A (en) | Fine diameter drawn yarn of polycyanoaryl ether and its production | |
| JP2752210B2 (en) | Polyether copolymer film | |
| JP2024070340A (en) | Polyphenylene Sulfide Film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210804 Address after: 610041 No. 4, unit 2, building 4, No. 60, Shuangnan section, Wuhou Avenue, Wuhou District, Chengdu, Sichuan Applicant after: Chen Jin Address before: 100089 No.048, g / F, block a, Zhizao street, Zhongguancun, 45 Chengfu Road, Haidian District, Beijing Applicant before: Beijing baiotake Technology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |