CN111978725A - Antibacterial high-temperature-aging-resistant polyimide film and preparation method thereof - Google Patents
Antibacterial high-temperature-aging-resistant polyimide film and preparation method thereof Download PDFInfo
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- CN111978725A CN111978725A CN202010735369.2A CN202010735369A CN111978725A CN 111978725 A CN111978725 A CN 111978725A CN 202010735369 A CN202010735369 A CN 202010735369A CN 111978725 A CN111978725 A CN 111978725A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 107
- 229920001721 polyimide Polymers 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 230000032683 aging Effects 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 23
- 239000004642 Polyimide Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000004381 surface treatment Methods 0.000 claims abstract description 19
- 238000007664 blowing Methods 0.000 claims abstract description 12
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 150000004985 diamines Chemical class 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- VPPHKHDARGZSFK-UHFFFAOYSA-N 5,5-bis(hydroxymethyl)imidazolidine-2,4-dione Chemical compound OCC1(CO)NC(=O)NC1=O VPPHKHDARGZSFK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 11
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 9
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
-
- 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
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
- C08K5/1539—Cyclic anhydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention relates to an antibacterial high-temperature-aging-resistant polyimide film and a preparation method thereof, wherein the preparation method comprises the following steps: (1) adding diamine and solvent, adding dianhydride and antibacterial functional monomer, and reacting for 10-24h to obtain polyamic acid containing antibacterial functional monomer；(2)SiO2Activating at 250-280 ℃ under the reflux of anhydrous toluene; then, performing surface treatment by using tridecafluorooctyltriethoxysilane; (3) maleic anhydride and SiO after surface treatment2Adding into polyamic acid, stirring for 2-3h, heating up in gradient, and performing thermal imidization to obtain polyimide; (4) adding nanometer TiO into polyvinyl alcohol colloidal solution with concentration of 10%2Stirring uniformly; (5) uniformly mixing the product obtained in the step (3) and the mixture obtained in the step (4), and granulating; (6) and blowing the film to form the polyimide film. In the invention, SiO is added into polyimide2、TiO2And an antibacterial functional monomer, and the obtained polyimide film has excellent high-temperature aging resistance and long-acting antibacterial property, and is suitable for food packaging under the condition of hotter weather in Africa.
Description
Technical Field
The invention belongs to the field of polyimide films, and particularly relates to an antibacterial high-temperature-aging-resistant polyimide film and a preparation method thereof.
Background
With the change of living habits of people, more and more fast-consumption foods are appeared, and the fast-consumption foods are used in food packaging films during storage and transportation. The packaging films currently used in the market are mainly polyethylene films. However, polyethylene is susceptible to aging caused by photo-oxidation, thermal oxidation and ozone decomposition under the action of the atmosphere, sunlight and oxygen, and is discolored, cracked, embrittled or pulverized, and loses mechanical properties. Moreover, the plasticity of the polyethylene film is greatly influenced by temperature, and the polyethylene film is easy to deform when exposed to high temperature, thereby greatly limiting the application of the polyethylene film as a packaging bag in high-temperature areas.
Polyimide has excellent heat resistance, mechanical properties, chemical resistance and other properties, and is widely used in aerospace field, electronic material field and the like, but polyimide films are hard and brittle, have insufficient strength, and are easy to age. The natural antibacterial agent has high safety but poor heat resistance and is easy to carbonize and decompose; the organic antibacterial agent has the defects of quick and high-efficiency sterilization, but poor long-acting property; the inorganic antibacterial agent has good long-term sterilization effect, but has slow antibacterial effect, and the silver and copper antibacterial agents have the problem of easy color change.
Disclosure of Invention
The invention aims to provide an antibacterial high-temperature-resistant aging-resistant polyimide film and a preparation method thereof, and aims to solve the problems in the prior art.
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, adding diamine and a solvent, adding dianhydride and an antibacterial functional monomer after complete ultrasonic dissolution, reacting for 10-24h, and then extracting bubbles in vacuum to obtain polyamide acid (PAA) containing the antibacterial functional monomer;
(2) adding silicon dioxide in argon protection, and activating at the temperature of 250-280 ℃ for 12-15h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane;
(3) adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into the polyamic acid obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient heating at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature.
The reaction temperature in the step (3) reaches 300 ℃, unfavorable conditions related to surface property such as swelling are easy to occur, and the phenomenon that the surface is easy to swell can be avoided by adding the maleic anhydride. Meanwhile, the maleic anhydride can improve TiO2And SiO2Compatibility with polyimide.
Preferably, the method further comprises the following steps:
(4) adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring;
(5) mixing the product obtained in the step (3) and the mixture obtained in the step (4) according to a mass ratio of 100: 1-2, mixing uniformly and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Preferably, the diamine in step (1) is 4,4' -oxydianiline; the dianhydride is one or more of bisphenol A type diether dianhydride, pyromellitic dianhydride and 4, 4-diphthalic dianhydride; the solvent is one or more of 4,4' -diaminodiphenyl ether, 2-butoxyethanol and dipropylene glycol monomethyl ether.
Preferably, the antibacterial functional monomer in the step (1) is dimethylol hydantoin; the content of the antibacterial functional monomer is 1-2% of the total mass of the antibacterial high-temperature-aging-resistant polyimide film.
Preferably, the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1-3% of the total mass of the antibacterial high-temperature aging resistant polyimide film.
Preferably, the addition amount of the maleic anhydride is 5-10% of the total mass of the antibacterial high-temperature aging resistant polyimide film.
Preferably, the silicon dioxide is nano silicon dioxide, and the particle size is 100-300 nm.
Preferably, the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide in the step (4) is 15-30: 1; the particle size of the nano titanium dioxide is 200-500 nm.
The antibacterial high-temperature-aging-resistant polyimide film prepared by the preparation method.
Preferably, the diamine in step (1) is 4,4' -oxydianiline; the dianhydride is one or more of bisphenol A type diether dianhydride, pyromellitic dianhydride and 4, 4-diphthalic dianhydride; the solvent is one or more of 4,4' -diaminodiphenyl ether, 2-butoxyethanol and dipropylene glycol monomethyl ether.
Preferably, the antibacterial functional monomer in the step (1) is dimethylol hydantoin; the content of the antibacterial functional monomer is 1-3% of the total mass of the antibacterial high-temperature-aging-resistant polyimide film.
Preferably, the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1-2% of the total mass of the antibacterial high-temperature aging resistant polyimide film.
Preferably, the addition amount of the maleic anhydride is 5-10% of the total mass of the antibacterial high-temperature aging resistant polyimide film.
The antibacterial high-temperature-aging-resistant polyimide film prepared by the preparation method.
The reactive antibacterial functional monomer is added in the preparation process, so that the antibacterial property is durable, and the long-acting antibacterial function can be achieved.
The polyvinyl alcohol side chain contains a large amount of-OH which can be wrapped on the surface of the nano titanium dioxide, so that the compatibility between the nano titanium dioxide and the polyimide is improved, the interface performance between the nano titanium dioxide and the polyimide is enhanced, the dispersion performance of the nano titanium dioxide is also improved, and the agglomeration is reduced.
The invention adopts a high-temperature activation method to ensure that the surface of the silicon dioxide contains a large amount of hydroxyl groups. The siloxy group of the tridecafluorooctyltriethoxysilane is easily hydrolyzed to become active silanol. The activated surface of the silicon dioxide containing a large amount of hydroxyl groups is subjected to surface treatment by the tridecafluorooctyl triethoxysilane, so that the dispersibility and compatibility of the silicon dioxide and the polyimide can be further improved, meanwhile, the tridecafluorooctyl triethoxysilane contains F, and fluorine atoms can improve the optical performance of the polyimide film.
Compared with the prior art, the invention introduces the nano SiO into the polyimide film2And nano TiO2，SiO2The toughness, weather resistance, wear resistance and ageing resistance of the polyimide can be obviously improved; TiO 22Has self-cleaning, antiseptic, antifungal, and ultraviolet resisting effects. In the preparation process, an antibacterial functional monomer is added and is inoculated into polyimide, so that the antibacterial property is durable; the addition of maleic anhydride can avoid the bubbling phenomenon on the surface and further improve TiO2And SiO2Compatibility with polyimide. The prepared food has excellent high-temperature aging resistance and long-acting antibacterial property, and is very suitable for food packaging under the condition of hotter weather in Africa.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings.
Example 1
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Adding silicon dioxide under the protection of argon, and activating at 280 ℃ for 12h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane;
(3) adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into polyamic acid containing the antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1 percent of the total mass of the antibacterial high-temperature aging resistant polyimide film. The addition of the maleic anhydride is 8 percent of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film; granulating;
(4) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Example 2
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Adding silicon dioxide under the protection of argon, and activating at 280 ℃ for 12h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane; the silicon dioxide is nano silicon dioxide with the particle size of 100-300 nm.
(3) Adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into polyamic acid containing the antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1 percent of the total mass of the antibacterial high-temperature aging resistant polyimide film. The addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film.
(4) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(5) Mixing the product obtained in the step (3) and the mixture obtained in the step (4) according to a mass ratio of 100: 1, uniformly mixing and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 1
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Adding maleic anhydride into the polyamic acid containing the antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, then performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; the addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film.
(3) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(4) Mixing the product obtained in the step (2) and the mixture obtained in the step (3) according to a mass ratio of 100: 1, uniformly mixing and granulating;
(5) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 2
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, performing ultrasonic dissolution completely, reacting for 15h, and then extracting bubbles in vacuum to obtain the polyamic acid.
(2) Adding silicon dioxide under the protection of argon, and activating at 280 ℃ for 12h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane; the silicon dioxide is nano silicon dioxide with the particle size of 100-300 nm.
(3) Adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into the polyamic acid obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1 percent of the total mass of the antibacterial high-temperature aging resistant polyimide film. The addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film.
(4) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(5) Mixing the product obtained in the step (3) and the mixture obtained in the step (4) according to a mass ratio of 100: 1, uniformly mixing and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 3
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, performing ultrasonic dissolution completely, reacting for 15h, and then extracting bubbles in vacuum to obtain the polyamic acid.
(2) Adding silicon dioxide under the protection of argon, and activating at 280 ℃ for 12h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane; the silicon dioxide is nano silicon dioxide with the particle size of 100-300 nm.
(3) Adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into the polyamic acid obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1 percent of the total mass of the antibacterial high-temperature aging resistant polyimide film. The addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film.
(4) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(5) And (3) mixing the product obtained in the step (3), the mixture obtained in the step (4) and dimethylolhydantoin according to the mass ratio of 100: 1: 1, uniformly mixing and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 4
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Adding silicon dioxide under the protection of argon, and activating at 280 ℃ for 12h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane; the silicon dioxide is nano silicon dioxide with the particle size of 100-300 nm.
(3) Adding the surface-treated silicon dioxide obtained in the step (2) into polyamic acid containing an antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, then performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1 percent of the total mass of the antibacterial high-temperature aging resistant polyimide film.
(4) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(5) Mixing the product obtained in the step (3) and the mixture obtained in the step (4) according to a mass ratio of 100: 1, uniformly mixing and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 5
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Carrying out surface treatment on silicon dioxide by using tridecafluorooctyltriethoxysilane; the silicon dioxide is nano silicon dioxide with the particle size of 100-300 nm.
(3) Adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into polyamic acid containing the antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the addition amount of the silicon dioxide subjected to surface treatment in the step (2) is 1 percent of the total mass of the antibacterial high-temperature aging resistant polyimide film. The addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film.
(4) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(5) Mixing the product obtained in the step (3) and the mixture obtained in the step (4) according to a mass ratio of 100: 1, uniformly mixing and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 6
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Adding maleic anhydride and silicon dioxide into polyamic acid containing an antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, then performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature; wherein the adding amount of silicon dioxide is 1 percent of the total mass of the antibacterial high-temperature-aging-resistant polyimide film. The addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film. The particle size of the silicon dioxide is 100-300 nm.
(3) Adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring; the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide is 20: 1; the particle size of the nano titanium dioxide is 200-500 nm.
(4) Mixing the product obtained in the step (2) and the mixture obtained in the step (3) according to a mass ratio of 100: 1, uniformly mixing and granulating;
(5) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
Comparative example 7
A preparation method of an antibacterial high-temperature-aging-resistant polyimide film comprises the following steps:
(1) under the protection of argon, firstly adding 4,4 '-oxydianiline and 4,4' -diaminodiphenyl ether solvent, after complete ultrasonic dissolution, adding pyromellitic dianhydride and dimethylolhydantoin, reacting for 15h, and then extracting bubbles in vacuum to obtain polyamic acid containing an antibacterial functional monomer; wherein the content of dimethylol hydantoin is 1 percent of the total mass of the antibacterial high-temperature-resistant and aging-resistant polyimide film.
(2) Adding maleic anhydride, silicon dioxide and nano titanium dioxide into polyamic acid containing an antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, then performing gradient heating at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, naturally cooling to room temperature, and granulating; wherein the adding amount of the silicon dioxide is 1 percent of the total mass of the antibacterial high-temperature-aging-resistant polyimide film, and the adding amount of the titanium dioxide is 1 percent of the total mass of the antibacterial high-temperature-aging-resistant polyimide film. The addition of the maleic anhydride is 8% of the total mass of the antibacterial high-temperature-resistant aging-resistant polyimide film. The particle size of the nano titanium dioxide is 200-500 nm. The particle size of the silicon dioxide is 100-300 nm;
(3) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
And (3) performance testing:
the antibacterial, high temperature aging resistant polyimide films prepared according to the preparation methods of examples 1 to 2 and comparative examples 1 to 7 were subjected to the following tests:
1. surface blistering
The polyimide film obtained in comparative example 4 had a significant bubbling on the surface, and none of the others.
2. Aging resistance
The antibacterial, high temperature aging resistant polyimide films of examples 1 to 2 and comparative examples 1 to 7 were prepared into food packaging bags, and irradiated with ultraviolet rays at 35 ℃ for 480 hours, with the results shown in table 1. As can be seen from the table, SiO was introduced into the polyimide film of the present invention2And TiO2And then, the anti-aging performance is better.
TABLE 1 comparison of aging Performance results for examples 1-2 and comparative examples 1-7
3. Mechanical Property test
The antibacterial high temperature aging resistant polyimide films of examples 1-2 and comparative examples 1-7 were subjected to 1500-hour photo aging (600Lux) tensile strength retention, elongation at break, tensile strength, glass transition temperature tests, and the results are shown in table 2. As can be seen from the table, the antibacterial high-temperature aging resistant polyimide film has the advantages of improved mechanical properties, obviously improved glass transition temperature and better high-temperature resistance.
TABLE 2 comparison of mechanical Properties of examples 1-2 and comparative examples 1-7
4. Test of antibacterial Property
The antibacterial high-temperature aging-resistant polyimide films of examples 1-2 and comparative examples 1-7 were prepared into food packaging bags, and the sterilization rate of the food packaging bags to escherichia coli and staphylococcus aureus was tested for 12 hours, and the test results are shown in tables 3 and 4. It can be seen from tables 3 and 4 that the polyimide film of the present invention has excellent antibacterial properties.
TABLE 3 comparison of the bactericidal ratio (%) of examples 1 to 2 and comparative examples 1 to 8 against E.coli
TABLE 4 comparison of Sterilization ratios (%) of examples 1 to 2 and comparative examples 1 to 8 against Staphylococcus aureus
Claims (9)
1. The preparation method of the antibacterial high-temperature-aging-resistant polyimide film is characterized by comprising the following steps of:
(1) under the protection of argon, adding diamine and a solvent, adding dianhydride and an antibacterial functional monomer after complete ultrasonic dissolution, reacting for 10-24h, and then extracting bubbles in vacuum to obtain polyamic acid containing the antibacterial functional monomer;
(2) adding silicon dioxide in argon protection, and activating at the temperature of 250-280 ℃ for 12-15h under the reflux of anhydrous toluene; performing surface treatment on the activated silicon dioxide by using tridecafluorooctyltriethoxysilane;
(3) adding maleic anhydride and the surface-treated silicon dioxide obtained in the step (2) into polyamic acid containing the antibacterial functional monomer obtained in the step (1), stirring for 2-3h, placing in an oven at 100 ℃ for 3h to remove a solvent in advance, performing gradient temperature rise at 140 ℃ for 1h, 180 ℃ for 1h, 260 ℃ for 2h and 300 ℃ for 2h, performing thermal imidization to obtain polyimide, and naturally cooling to room temperature.
2. The method of claim 1, further comprising:
(4) adding nanometer titanium dioxide into polyvinyl alcohol colloidal solution with the concentration of 10%, and uniformly stirring;
(5) mixing the product obtained in the step (3) and the mixture obtained in the step (4) according to a mass ratio of 100: 1-2, mixing uniformly and granulating;
(6) and blowing the film to form the antibacterial high-temperature-resistant aging-resistant polyimide film.
3. The production method according to claim 1, wherein the diamine in the step (1) is 4,4' -oxydianiline; the dianhydride is one or more of bisphenol A type diether dianhydride, pyromellitic dianhydride and 4, 4-diphthalic dianhydride; the solvent is one or more of 4,4' -diaminodiphenyl ether, 2-butoxyethanol and dipropylene glycol monomethyl ether.
4. The preparation method according to claim 1, wherein the antibacterial functional monomer in step (1) is dimethylolhydantoin; the content of the antibacterial functional monomer is 1-2% of the total mass of the antibacterial high-temperature-aging-resistant polyimide film.
5. The preparation method according to claim 1, wherein the addition amount of the surface-treated silica obtained in the step (2) is 1-3% of the total mass of the antibacterial high-temperature aging-resistant polyimide film.
6. The preparation method according to claim 1, wherein the addition amount of the maleic anhydride is 5-10% of the total mass of the antibacterial high-temperature aging resistant polyimide film.
7. The method as claimed in claim 1, wherein the silica is nano silica with a particle size of 100-300 nm.
8. The preparation method according to claim 2, wherein the mass ratio of the 10% polyvinyl alcohol colloidal solution to the nano titanium dioxide in the step (4) is 15-30: 1; the particle size of the nano titanium dioxide is 200-500 nm.
9. The antibacterial high-temperature aging resistant polyimide film prepared according to the preparation method of claim 1.
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