CN113817218A - Biopolymer composite membrane and preparation method thereof - Google Patents
Biopolymer composite membrane and preparation method thereof Download PDFInfo
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- CN113817218A CN113817218A CN202011562157.5A CN202011562157A CN113817218A CN 113817218 A CN113817218 A CN 113817218A CN 202011562157 A CN202011562157 A CN 202011562157A CN 113817218 A CN113817218 A CN 113817218A
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- polymer
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- biopolymer
- film
- solution
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 229920001222 biopolymer Polymers 0.000 title claims abstract description 55
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- -1 soy protein isolate Polymers 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 108010010803 Gelatin Proteins 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 14
- 229920000159 gelatin Polymers 0.000 claims abstract description 14
- 239000008273 gelatin Substances 0.000 claims abstract description 14
- 235000019322 gelatine Nutrition 0.000 claims abstract description 14
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 13
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920001661 Chitosan Polymers 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229920005610 lignin Polymers 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229940071440 soy protein isolate Drugs 0.000 claims abstract description 9
- 239000008107 starch Substances 0.000 claims abstract description 9
- 235000019698 starch Nutrition 0.000 claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 102000008186 Collagen Human genes 0.000 claims abstract description 5
- 108010035532 Collagen Proteins 0.000 claims abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 5
- 229940072056 alginate Drugs 0.000 claims abstract description 5
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 5
- 229920000615 alginic acid Polymers 0.000 claims abstract description 5
- 229920001436 collagen Polymers 0.000 claims abstract description 5
- 239000001814 pectin Substances 0.000 claims abstract description 5
- 235000010987 pectin Nutrition 0.000 claims abstract description 5
- 229920001277 pectin Polymers 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 78
- 230000000844 anti-bacterial effect Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004631 polybutylene succinate Substances 0.000 claims description 8
- 229920002961 polybutylene succinate Polymers 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000013538 functional additive Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 5
- 239000003899 bactericide agent Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 239000004633 polyglycolic acid Substances 0.000 claims description 5
- 239000004626 polylactic acid Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000003925 fat Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 14
- 239000012466 permeate Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 60
- 238000003756 stirring Methods 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 15
- 230000035699 permeability Effects 0.000 description 14
- 239000008213 purified water Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 229920005552 sodium lignosulfonate Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 210000004243 sweat Anatomy 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 108060008539 Transglutaminase Proteins 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 102000003601 transglutaminase Human genes 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940001941 soy protein Drugs 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 208000008454 Hyperhidrosis Diseases 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910018828 PO3H2 Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 206010039897 Sedation Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 230000036280 sedation Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 208000013460 sweaty Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D197/00—Coating compositions based on lignin-containing materials
- C09D197/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
Abstract
The application provides a biopolymer composite membrane and a preparation method thereof, wherein the method comprises the following steps: s1, dispersing the biopolymer into a solvent to prepare a polymer solution; the solvent is preferably water or a polar solvent; s2, coating the polymer solution on the surface of a microporous substrate to form a wet film, and drying to obtain a biopolymer composite film; the biopolymer is selected from at least two of lignin salt, starch and derivatives thereof, carboxymethyl cellulose, gelatin, pectin, collagen, soy protein isolate, chitosan and derivatives thereof, alginate, polyacrylic acid, polyethylene oxide and polyvinyl alcohol resin, and is used for forming a film layer having barrier property but selectively permeable to water molecules. The biopolymer composite membrane prepared by the invention can selectively permeate water molecules, can block other substances such as gas and the like, has good biocompatibility and has wide application prospect.
Description
Technical Field
The application relates to the technical field of membrane materials, in particular to a biopolymer composite membrane and a preparation method thereof.
Background
The materials of the film type have wide application in many fields such as daily use, industry, medical treatment, military and the like, and specific applications of the film material are presented as follows:
1. protective articles for daily use, special industries, medical and even military use aim to protect personnel from the effects and hazards of different severe environments, but because of the requirement of good insulation performance, the outward transmission of human body heat and moisture is limited at the same time, and the effects are reflected in the protective articles by sacrificing a certain degree of comfort. Currently, the most significant comfort problem with personal protective products is caused by the lack of water vapor permeability. In particular for high performance protective articles, since protection against harmful substances means that the materials used are completely liquid-tight and sometimes even gas-tight. Despite their high protective properties, their comfort is often very unsatisfactory, and when used in adverse working conditions or for extended periods of time, the temperature and humidity inside the protective article can increase, causing irritation to the skin in addition to discomfort, and the body inside the protective garment can sweat in large amounts that cannot be removed, causing the wearer to be exposed to sweaty conditions for extended periods of time, easily causing various illnesses and discomfort.
2. In the food packaging industry, the requirements and purposes for different food packaging materials vary. In the food packaging with the moisture-removing function while the gas is required to be blocked, for example, the existing film material is difficult to combine the functions in the transportation and storage of fresh fish meat and the like.
With the rapid development of society, the living standard of people is gradually improved, and the market for creating efficient and comfortable consumer products needs a lot of (new) functional intelligent materials. How to improve the use comfort of protective articles, remove the uncomfortable feeling of the existing articles or the dominant and recessive pain points, and how to develop a multifunctional brand new film material product which can permeate water and block other substances in a broad sense is one of the problems to be solved in the industry at present.
Disclosure of Invention
In order to solve the problems, the invention provides a biopolymer composite membrane and a preparation method thereof.
The invention provides a preparation method of a biopolymer composite membrane, which comprises the following steps:
s1, dispersing the biopolymer into a solvent to prepare a polymer solution; the solvent is preferably water or a polar solvent;
s2, coating the polymer solution on the surface of a microporous substrate to form a wet film, and drying to obtain a biopolymer composite film;
the biopolymer is selected from at least two of lignin salt, starch and derivatives thereof, carboxymethyl cellulose, gelatin, pectin, collagen, soy protein isolate, chitosan and derivatives thereof, alginate, polyacrylic acid, polyethylene oxide and polyvinyl alcohol resin, and is used for forming a film layer having barrier property but selectively permeable to water molecules.
Preferably, the biopolymer is selected from at least two of lignin salt, carboxymethyl cellulose, gelatin, chitosan, soy protein isolate, polyacrylic acid, and polyvinyl alcohol resin; the mass percentage of the biological polymer in the polymer solution is 2-25%.
Preferably, the polar solvent is selected from one or more of ethanol, n-propanol, isopropanol, butanol, ethyl acetate, tetrahydrofuran and acetonitrile.
Preferably, the microporous substrate is a polymer microporous substrate, a ceramic microporous substrate or a metal microporous substrate; the polymer microporous substrate is preferably a polymer non-woven material, a polymer breathable film, a polymer hollow fiber ultrafiltration membrane, a polymer microporous pipe or a polymer microporous plate; the metal microporous base material is preferably an aluminum microporous film, an aluminum microporous plate, a stainless steel microporous film or a stainless steel microporous plate.
Preferably, the macromolecule in the macromolecule microporous substrate is selected from one or more of polyethylene, polypropylene, polyurethane, polyamide, polyester, polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, cellulose, starch, polylactic acid, polybutylene succinate, polyhydroxylated fats, polyglycolic acid and polycaprolactone.
Preferably, the method further comprises the following steps of: and adding the functional auxiliary agent into the polymer solution to prepare a composite solution.
Preferably, the functional assistant is at least one selected from an antibacterial bactericide, a thickening agent, a penetrating agent and a cross-linking agent, and the mass percentage of the functional assistant in the composite solution is preferably 0.01-5%.
Preferably, the functional assistant is a metal nano polyoxide or nano metal loaded graphene material, and the mass percentage of the functional assistant in the composite solution is preferably 0.01-3%.
Preferably, the thickness of the wet film is 4-100 microns; the drying temperature is 20-120 ℃.
The invention provides a biopolymer composite membrane prepared by the preparation method.
Compared with the prior art, the invention selects at least two specific biopolymers, and forms a film layer with barrier property but capable of selectively permeating water molecules on the surface of the microporous substrate through different coating processes such as roller coating, spraying or printing, so as to obtain the biopolymer composite film. The biopolymer composite membrane prepared by the invention can selectively permeate water molecules, can block other substances such as gas and the like, and can be widely applied to the fields of daily use, industry, medical treatment and the like. In addition, because the natural or water-soluble biopolymer is adopted, the composite film material has good biocompatibility, is biodegradable and is beneficial to environmental protection.
Furthermore, the invention can use water as solvent, uses little or no toxic organic solvent and has better environmental protection property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention.
The embodiment of the application provides a preparation method of a biopolymer composite membrane, which comprises the following steps:
s1, dispersing the selected biopolymer into a solvent, wherein the solvent is preferably water or a polar solvent, and preparing to obtain a polymer solution;
optionally adding different kinds of functional additives into the prepared polymer solution to prepare a composite solution;
s2, coating the prepared polymer solution or composite solution on the surface of the selected microporous substrate to form a wet film, and drying to obtain the biopolymer composite film;
the biopolymer is selected from at least two of lignin salt, starch and derivatives thereof, carboxymethyl cellulose, gelatin, pectin, collagen, soy protein isolate, chitosan and derivatives thereof, alginate, polyacrylic acid, polyethylene oxide and polyvinyl alcohol resin, and is used for forming a film layer having barrier property but selectively permeable to water molecules.
The biopolymer composite membrane prepared by the invention can selectively permeate water molecules, can block other substances such as gas and the like, has good biocompatibility and has wide application prospect.
In the embodiment of the invention, various selected biopolymers can be respectively dissolved to prepare solutions, and then the solutions are uniformly mixed to obtain the polymer solution.
In the present invention, the biopolymer is a renewable, environmentally friendly and biodegradable material, and different biopolymers, i.e., water-soluble environmentally friendly polymers, biomaterials chemically produced from natural resources or polymers biosynthesized from living bodies. The biopolymer selected by the invention is at least two of lignin salt, starch and derivatives thereof, carboxymethyl cellulose, gelatin, pectin, collagen, soy protein isolate, chitosan and derivatives thereof, alginate, polyacrylic acid, polyethylene oxide and polyvinyl alcohol resin, preferably at least two of lignin salt, carboxymethyl cellulose, gelatin, chitosan, soy protein isolate, polyacrylic acid and polyvinyl alcohol resin, and can be matched to form a film layer which selectively permeates water molecules and blocks other substances such as gas, namely the film layer is airtight and has the dynamic moisture permeability effect.
The invention utilizes the unique performance of various biological materials to embody the characteristics of the membrane material, and the membrane material can be regarded as a skin-like material for easier understanding. The human skin can automatically adjust the barrier and permeability according to different environments; the water permeable channel constructed by the composite membrane material of the invention dynamically changes under different temperature and humidity conditions, so that the water passing efficiency is obviously changed correspondingly.
Specifically, the high molecular weight polymers (synthetic or biological polymers) selected for use herein contain a plurality of polar functional groups: -OH, -SH, -COOH, -OR, -COOR, -PO3H2、-SO3H and-NH2And the like, and then the polar group functional groups and various functional auxiliary agents are used for organic integration and blending to build a water permeable (moisture conducting) channel with reinforced hydrophilic-hydrophobic groups. This construction mode is different from the commonly understood brick fixing tunnel wall for covering tunnel, the film material of the present application is influenced by the ambient temperature and humidity during the use process, and the internal structure of the film material is dynamically changed through the effective chemical bond linkage of hydrogen bond, ionic bond and/or covalent bond.
For example, as the humidity and the temperature increase, the efficiency of water molecules passing through the membrane material increases, which reflects that the reinforced water permeable channels composed of polar hydrophilic groups and non-polar hydrophobic groups are closely related to the temperature and the humidity, and especially when the ambient temperature is high, more water permeable channels are dynamically formed to convey water molecules to the opposite side of the membrane.
In some examples, in the humidity range of 20% -60% and without external pressure, if the temperature is low, such as 20 ℃, the passing rate level of water molecules passing through the membrane material autonomously is basically stable, because at this temperature, chemical bond linkage is stable, and the formed water permeable channel is not affected by high or low humidity of the environment on the water molecule output side; at moderate temperatures, such as 25 ℃, chemical bonding can easily change, and the water permeable channels change, so that the water molecules will pass at a higher rate when moving to the side of the membrane with lower relative humidity, and at a lower rate when moving to the side of the membrane with higher relative humidity.
Among them, the lignin salt is generally a lignin sulfonate such as sodium lignin sulfonate; resins such as polyacrylic acid are water soluble or can be chemically produced from natural sources. The molecular weight range of the selected biopolymer is 5000-5000000; at least two of the materials are selected to be matched according to a certain proportion, so that the material can block most of the materials and has excellent performance of penetrating moisture. In some embodiments of the invention, the biopolymers selected for use include sodium lignosulfonate, carboxymethyl cellulose, and polyacrylic acid; in other embodiments, sodium lignosulfonate, carboxymethyl cellulose and polyvinyl alcohol are used. Also, the mass percentage of biopolymer in the polymer solution may be 2% to 25%, preferably 5% to 25%, such as 10%, 12%, 15%, 16%, 18%, 20%, 21%, 24%.
The embodiment of the invention can dissolve selected biological polymers in an aqueous medium at a constant temperature selected from the range of 10-100 ℃ for a predetermined time and in a predetermined sequence to form a solution, and fully stir the solution to dissolve and mix the biological polymers uniformly. Wherein the solvent can be purified water, or polar solvent selected from one or more of ethanol, n-propanol, isopropanol, butanol, ethyl acetate, tetrahydrofuran and acetonitrile.
Chemical reactions currently used to manufacture important compounds (e.g., drugs) are essentially always performed in solution, as are research efforts to invent new compounds and develop appropriate methods to make them. In the past, and continuing until now, the solvents used have typically been Volatile Organic Compounds (VOCs), which have presented environmental concerns. Their evaporation in air can cause the greenhouse effect which causes global warming, and in some cases, solvent evaporating vapors can catalytically destroy the ozone layer responsible for protecting the earth and its inhabitants from short-wave ultraviolet solar radiation; such vapors may also be toxic to humans, plants, or animals, or may cause illness. Therefore, the invention preferably uses water as a solvent, and uses little or no toxic organic solvent.
The invention selects the biological polymer in a sustainable mode, and compared with an oil-based polymer material, the biological polymer not only can bring competitive advantages in the aspect of environmental protection, but also has unique properties which cannot be imitated by the conventional polymer. However, biopolymers generally have poor mechanical properties, short fatigue life, low chemical resistance, poor long-term durability and limited processability, leading to major limitations for their industrial use.
According to different functional requirements, functional (functional) auxiliaries (organic or inorganic fillers, antibacterial bactericides and the like) are optionally added into the solution obtained in the previous step, and the mixture is fully stirred to be uniformly mixed, so that a composite solution is obtained.
In the embodiment of the invention, the functional assistant may be an organic or inorganic functional additive material selected from at least one of an antibacterial bactericide, a thickener, a penetrant and a cross-linking agent; or nano-scale functional materials, or can be selected together. Wherein, the nanometer functional material can be metal nanometer polyoxide, such as zinc, titanium or copper polyoxide modified by noble metal; or the graphene material can be a nanoscale metal-loaded graphene material, including a graphene material loaded with noble metal silver, platinum or palladium. Specifically, the embodiment of the invention can adopt the nano titanium dioxide alone or jointly select the nano titanium dioxide and at least one of the materials such as the antibacterial bactericide, the coupling agent, the graphene and the like.
In some embodiments of the present invention, the mass percentage of the functional additive (functional additive) in the composite solution is preferably 0.01% to 5%, more preferably 0.05% to 4%, and even more preferably 0.1% to 3%; in other embodiments, the mass percentage of the functional additive (nanoscale functional material) in the composite solution is preferably 0.01% to 3%, more preferably 0.05% to 2.5%, and even more preferably 0.1% to 2%. The embodiment of the invention utilizes the unique performance of various biological materials to embody the characteristics of the membrane material as much as possible, thereby avoiding adding chemical additives as much as possible.
In the embodiment of the invention, the prepared polymer or composite solution is applied to one surface or two surfaces of the microporous base material by various optional coating processes at the temperature of 10-200 ℃, so as to obtain the composite membrane material.
In the invention, the microporous base material is a base material with certain micropores, and can play a supporting role for a membrane layer formed by various biopolymers. From the aspect of material, the microporous base material can be a macromolecular microporous base material, a ceramic microporous base material or a metal microporous base material. The microporous substrate has a pore size of 0.1-3 microns, a porosity of 35-90%, preferably 60-90%, and a thickness of 10-350 microns.
Wherein, the macromolecule in the macromolecule microporous substrate can be a conventional polymer, and can also be a polymer with biocompatibility; specifically, the material may be selected from one or more of polyethylene, polypropylene, polyurethane, polyamide (nylon), polyester (mainly polyethylene terephthalate including polyethylene terephthalate), polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, cellulose, starch, polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxylated fats (PHAs), polyglycolic acid, and polycaprolactone. Structurally, the microporous polymer substrate may include non-woven polymer material, breathable polymer film, hollow polymer fiber ultrafiltering film, microporous polymer pipe or microporous polymer board. Further, the metal-based microporous substrate is preferably an aluminum microporous film, an aluminum microporous plate, a stainless steel-based microporous film, or a stainless steel-based microporous plate.
In some embodiments of the present invention, the microporous substrate is a polymeric nonwoven material, such as a polypropylene microporous substrate, a meltblown composite breathable nonwoven material, wherein the polymeric material comprises polypropylene, polyurethane, polyamide, polyester, polysulfone, and a biocompatible nanofiber membrane, such as polylactic acid (PLA), polybutylene succinate (PBS), Polyhydroxylipids (PHAs), polyglycolic acid, and polycaprolactone or a copolymer of two or more polymers.
In other embodiments of the present invention, the microporous substrate is a gas permeable membrane, a hollow fiber ultrafiltration membrane, a tube or a plate made of a polymer material including polyethylene, polypropylene, polyurethane, polyamide, polysulfone, polyvinylidene fluoride, polyethylene terephthalate, polytetrafluoroethylene, cellulose, polyether sulfone, and a biocompatible nanofiber membrane such as starch compound, polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxylated fats (PHAs), polyglycolic acid, and polycaprolactone, or a copolymer of two or more polymers.
According to the embodiment of the invention, the surface of the microporous substrate can be coated to form a wet film containing the composite solution, and the wet film is dried to obtain the composite film material with the dynamic moisture permeability effect and air tightness. Wherein, the thickness of the wet film is generally 4 to 100 micrometers. The drying mode can be drying at room temperature, and other modes such as drying can also be adopted, the temperature can be 20-120 ℃, and the thickness of the wet film after drying is 1-50 microns.
The invention provides a biopolymer composite membrane, which is prepared by the preparation method; the composite membrane comprises a microporous substrate, and at least one biopolymer membrane layer is coated and compounded on the surface of the microporous substrate, wherein the biopolymer membrane layer is preferably formed by the aqueous solution containing a plurality of biopolymers.
The biopolymer composite membrane prepared by the invention can selectively permeate water molecules, can block other substances such as gas and the like, and can be widely applied to the fields of daily use, industry, medical treatment and the like.
For example, in the field of protective product applications, in order to achieve a good balance between the extreme requirements of protection and comfort, the moisture permeability of the composite film material of the present invention can improve comfort, and sweat discharged by a wearer due to hot or mental use can reach the surface of the fabric more quickly after seeping out of the skin. The material of the invention attached to the surface of the material can continuously discharge sweat in the form of water molecules into the air at a satisfactory speed in the state of water molecules. Moreover, the membrane material is airtight, so that the air tightness of the material is maintained or increased in a proper amount while the heat and sweat accumulated in the body are transmitted to the environment, and the isolation safety is further ensured. In addition, after the antibacterial and bactericidal functional material is added, the antibacterial and bactericidal fabric has the functions of killing a large number of bacteria such as glucose chain bacteria, escherichia coli and the like, and can kill bacteria, reduce diseases and reduce peculiar smell while perspiring.
In the field of food packaging, gas is required to be blocked, and meanwhile, in food packaging with a moisture-discharging function, such as packaging of fresh fish meat and the like in transportation and storage, the invention has unique advantages: when the humidity is discharged, the gas water in molecular state is separated out from the air, but not the liquid water, and the oxygen and the like are blocked, so that the freshness can be kept to the maximum extent and the transportation and storage space is not polluted.
The composite membrane has the bionic characteristic similar to skin, can replace bandage adhesive plaster and the like to protect injured skin, can discharge precipitates of wounds while sterilizing and blocking gas, keeps the proper humidity of the wounds, and is beneficial to reducing infection and accelerating healing. Because the liquid water is separated out as gaseous molecules to absorb heat, the invention is suitable for non-icing and non-cold water-soaking physical thermal applications, such as fever reduction patches, post-art sedation patches and the like. The film material of the invention can be used for moisturizing skin while cooling, can be stored in a dry state, and can be used as a functional mask after being watered.
In addition, the invention can also be used as a molecular humidifier imitating natural climate conditions, a dehydration treatment membrane material in food and medicine industries, and a fabric used for sportswear, special tools (such as steel mills, field police, military uniforms, outdoor clothes), underwear and the like.
The composite film material of the present invention can dynamically permeate moisture and block a large number of other substances, and has a broad spectrum of applications, including but not limited to the specific applications described above. The film material is green and environment-friendly, and has wide application prospect.
In order to further understand the present application, the biopolymer composite membrane and the method for preparing the same provided in the present application are specifically described below with reference to examples.
The performance test of the membrane material is carried out according to the method requirements of ASTM F1249 and GB 19082-2009 medical disposable protective clothing technology; the moisture permeability and the antibacterial and bacteriostatic properties of the film material are determined by a standardized test method.
Example 1
(1) Preparing 10% sodium lignosulfonate water solution with purified water at room temperature of 20 ℃, and uniformly stirring until the sodium lignosulfonate water solution is completely dissolved.
(2) Preparing 3% carboxymethyl cellulose aqueous solution with purified water at room temperature of 20 ℃, and fully and uniformly stirring for later use.
(3) A5% aqueous solution of polyacrylic acid (average molecular weight: 80 ten thousand) was prepared with purified water at room temperature of 20 ℃ and dissolved with stirring.
(4) Uniformly mixing the solutions prepared in the steps (1), (2) and (3) according to the weight ratio of 1:1:1, and then stirring for 3 hours at the temperature of 45-50 ℃.
(5) And (4) applying the solution obtained in the step (4) on the surface of a polypropylene microporous substrate to form a wet polymer film, and airing at room temperature to obtain the biopolymer composite film.
Wherein, the thickness of the polymer wet film is 6 microns, and the thickness of the film layer after drying at room temperature is 1-2 microns.
Through tests, the moisture permeability of the obtained film material is as follows: 8400g/m224hr @30 ℃; breaking strength and elongation of 95N and 183% in the machine direction and 87N and 180% in the transverse direction. The obtained composite film material has excellent performance.
Example 2
(1) Preparing 15% sodium lignosulfonate water solution with purified water at room temperature of 20 ℃, and stirring until the sodium lignosulfonate water solution is completely dissolved.
(2) Preparing 5% carboxymethyl cellulose aqueous solution with purified water at room temperature of 20 ℃, and fully and uniformly stirring for later use.
(3) Preparing 6% polyvinyl alcohol aqueous solution with purified water at room temperature of 20 ℃, and stirring for dissolving for later use.
(4) Uniformly mixing the solutions prepared in the steps (1), (2) and (3) according to the weight ratio of 1:1:1, and then stirring for 3 hours at the temperature of 45-50 ℃.
(5) And (4) applying the solution obtained in the step (4) on the surface of a polypropylene microporous substrate to form a wet polymer film, and airing at room temperature to obtain the biopolymer composite film.
Wherein, the thickness of the wet film is 6 microns, and the thickness of the dried film layer is 1-2 microns.
Through tests, the moisture permeability of the obtained film material is as follows: 9144g/m224hr @30 ℃; the breaking strength and elongation were 94N and 189% in the machine direction and 80N and 178% in the transverse direction. The obtained composite film material has excellent performance.
Example 3
(1) Preparing 5% gelatin water solution with purified water at room temperature of 20 deg.C, and stirring thoroughly.
(2) 8g of 10% sodium lignosulfonate aqueous solution and 5 g of 5% gelatin aqueous solution prepared above are stirred and mixed evenly at room temperature of 20 ℃.
(3) And (3) sequentially adding 0.1 g of nano-scale titanium dioxide and 0.35 g of silane coupling agent A-171 into the solution prepared in the step (2) step by step at room temperature of 20 ℃, uniformly mixing, and continuously stirring for 5 hours at the temperature of 50-60 ℃.
(4) And (4) applying the solution obtained in the step (3) on the surface of a polypropylene microporous substrate to form a wet film of the composite solution, and airing at room temperature to obtain the biopolymer composite film.
Wherein, the thickness of the wet film of the composite solution is 6 microns, and the thickness of the dried film is 1-2 microns.
Through tests, the moisture permeability of the obtained film material is as follows: 8808g/m224hr @30 ℃; tenacity at break and elongation were 98N and 190% in the machine direction and 84N and 183% in the transverse direction. The obtained composite film material has excellent performance.
Example 4
(1) Weighing 4g of isolated soy protein at room temperature of 20 ℃, adding the isolated soy protein into 80 g of purified water, stirring, adjusting the pH value to 2 by using 10% hydrochloric acid solution, stirring for one hour at room temperature of 20 ℃, heating to 75-80 ℃ by using a water bath, and then heating and stirring for one hour. The solution was filtered through a 120 mesh nylon mesh to obtain a solution having a solid content of 3.5%.
(2) Preparing 5% gelatin water solution with purified water at room temperature of 20 deg.C, and stirring thoroughly.
(3) Preparing 2% transglutaminase (micro transglutaminase) aqueous solution with purified water at room temperature of 20 deg.C, and stirring for dissolving.
(4) Slowly and uniformly mixing a 5% polyacrylic acid (average molecular weight: 80 ten thousand) aqueous solution and the solutions prepared in the steps (1) to (3) according to the weight ratio of 1:1 at room temperature and 20 ℃, and continuously stirring for 4 hours at the temperature of 50-60 ℃.
(5) And (4) applying the solution obtained in the step (4) on the surface of a polypropylene microporous substrate to form a wet film, and airing at room temperature to obtain the biopolymer composite film.
Through testing, the moisture permeability of the obtained film material is 9552g/m224hr @30 ℃; tenacity at break and elongation were 97N and 188% in the machine direction and 81N and 182% in the transverse direction. The obtained composite film material has excellent performance.
Example 5
(1) Weighing 4g of soy protein isolate, adding into 80 g of purified water, stirring, adjusting pH to 10 with 30% sodium hydroxide solution, stirring for one hour at room temperature of 20 ℃, heating to 75-80 ℃ with a water bath, and then heating and stirring for one hour. The solution was filtered through a 120 mesh nylon mesh to obtain a solid content of 3.7%.
(2) Preparing 2% chitosan water solution with purified water at room temperature of 20 deg.C, and stirring thoroughly until completely dissolved.
(3) And (3) slowly and uniformly mixing a 5% gelatin aqueous solution, a 5% polyvinyl alcohol aqueous solution and a 2% transglutaminase aqueous solution with the solutions prepared in the steps (1) and (2) according to the weight ratio of 1:1, and stirring for 4 hours at 50-60 ℃.
(4) And (3) applying the solution obtained in the step (3) on the surface of the melt-blown composite breathable non-woven fabric material (the smoother surface) to form a wet film, and airing at room temperature to obtain the composite film.
Wherein, the thickness of the wet film of the composite solution is 6 microns, and the thickness of the dried film layer is 1-2 microns.
The moisture permeability of the obtained film material is 6000g/m through testing2·24hr@30℃；410g/m2Hr @38 ℃; tenacity at break and elongation were 108N and 189% in the machine direction and 56N and 197% in the transverse direction. The obtained composite film material has excellent performance.
Example 6
(1) 10 g of a 5% aqueous solution of polyacrylic acid (average molecular weight: 80 ten thousand), 5 g of a 5% aqueous solution of gelatin and 3 g of a 5% aqueous solution of carboxymethyl cellulose were mixed in this order at room temperature of 20 ℃ and stirred uniformly.
(2) 0.1 g of nano-scale titanium dioxide is weighed and added into the solution, the mixture is stirred evenly and then is stirred for 3 hours at the temperature of 50-60 ℃.
(3) And (3) applying the solution obtained in the step (2) on the surface of the melt-blown composite breathable non-woven fabric material (the smoother surface) to form a wet film, and airing at room temperature to obtain the biopolymer composite film.
Wherein, the thickness of the wet film of the composite solution is 6 microns, and the thickness of the dried film layer is 1-2 microns.
The moisture permeability of the obtained film material is 6120g/m through testing2·24hr@30℃；422g/m2Hr @38 ℃; tenacity at break and elongation were 110N and 190% in the machine direction and 67N and 194% in the cross direction. The obtained composite film material has excellent performance.
Example 7
(1) 8g of 5 percent polyvinyl alcohol solution, 5 g of 5 percent gelatin water solution, 1 g of carboxymethyl cellulose and 1 g of 10 percent sodium lignosulfonate are mixed and stirred evenly at room temperature of 20 ℃.
(2) 0.1 g of nano-scale titanium dioxide and 0.05 g of silver-loaded graphene material are weighed and sequentially added into the solution, fully stirred and uniformly mixed.
(3) 0.30 g of the fungicide KIL-350 (Kyoho, Guangzhou) and 0.25 g of the silane coupling agent A-171 were weighed out and added to the solution obtained in step (2) in this order, mixed well, and then stirred at 50 to 60 ℃ for 5 hours.
(4) And (4) applying the solution obtained in the step (3) on the surface of a polypropylene microporous substrate to form a wet film, and drying at room temperature to obtain the biopolymer composite film.
Wherein, the thickness of the wet film of the composite solution is 6 microns, and the thickness of the dried film layer is 1-2 microns.
Through testing, the moisture permeability of the obtained film material is 9792g/m224hr @30 ℃; the breaking strength and elongation were 93N and 189% in the machine direction and 86N and 183% in the transverse direction. Antibacterial rate 99.9% (JIS Z2801: 2010 standard)
Mildew resistance grade 0 (ASTM G21-15 standard). The obtained composite film material has excellent performance.
From the above embodiments, the invention selects at least two specific biopolymers, and forms a barrier film layer capable of selectively permeating water molecules on the surface of the microporous substrate by different coating processes such as roll coating, spray coating or printing, so as to obtain the biopolymer composite film. The biopolymer composite membrane prepared by the invention can selectively permeate water molecules (namely dynamic moisture permeability), can block other substances such as gas and the like, and can be widely applied to the fields of daily use, industry, medical treatment and the like. In addition, because the natural or water-soluble biopolymer is adopted, the composite film material has good biocompatibility, is biodegradable and is beneficial to environmental protection. Furthermore, the invention can use water as solvent, uses little or no toxic organic solvent and has better environmental protection property.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. A preparation method of a biopolymer composite membrane comprises the following steps:
s1, dispersing the biopolymer into a solvent to prepare a polymer solution; the solvent is preferably water or a polar solvent;
s2, coating the polymer solution on the surface of a microporous substrate to form a wet film, and drying to obtain a biopolymer composite film;
the biopolymer is selected from at least two of lignin salt, starch and derivatives thereof, carboxymethyl cellulose, gelatin, pectin, collagen, soy protein isolate, chitosan and derivatives thereof, alginate, polyacrylic acid, polyethylene oxide and polyvinyl alcohol resin, and is used for forming a film layer having barrier property but selectively permeable to water molecules.
2. The method of claim 1, wherein the biopolymer is selected from at least two of lignin salt, carboxymethyl cellulose, gelatin, chitosan, soy protein isolate, polyacrylic acid, and polyvinyl alcohol resin; the mass percentage of the biological polymer in the polymer solution is 2-25%.
3. The method according to claim 1, wherein the polar solvent is one or more selected from the group consisting of ethanol, n-propanol, isopropanol, butanol, ethyl acetate, tetrahydrofuran, and acetonitrile.
4. The method of claim 1, wherein the microporous substrate is a polymeric microporous substrate, a ceramic microporous substrate, or a metal-based microporous substrate; the polymer microporous substrate is preferably a polymer non-woven material, a polymer breathable film, a polymer hollow fiber ultrafiltration membrane, a polymer microporous pipe or a polymer microporous plate; the metal microporous base material is preferably an aluminum microporous film, an aluminum microporous plate, a stainless steel microporous film or a stainless steel microporous plate.
5. The method according to claim 4, wherein the polymer in the microporous polymer substrate is selected from one or more of polyethylene, polypropylene, polyurethane, polyamide, polyester, polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, cellulose, starch, polylactic acid, polybutylene succinate, polyhydroxylated fats, polyglycolic acid, and polycaprolactone.
6. The method of any one of claims 1-5, further comprising, prior to coating: and adding the functional auxiliary agent into the polymer solution to prepare a composite solution.
7. The preparation method according to claim 6, wherein the functional adjuvant is at least one selected from an antibacterial bactericide, a thickening agent, a penetrating agent and a cross-linking agent, and the mass percentage of the functional adjuvant in the composite solution is preferably 0.01-5%.
8. The preparation method according to claim 6, wherein the functional additive is a metal nano polyoxide or nano metal loaded graphene material, and the mass percentage of the functional additive in the composite solution is preferably 0.01% to 3%.
9. The production method according to any one of claims 1 to 5, wherein the wet film has a thickness of 4 to 100 μm; the drying temperature is 20-120 ℃.
10. A biopolymer composite membrane produced by the production method according to any one of claims 1 to 9.
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| CN115895011A (en) * | 2022-10-25 | 2023-04-04 | 大连工业大学 | Preparation method of biodegradable black mulching film |
| CN116041776A (en) * | 2022-11-01 | 2023-05-02 | 巴斯特医药科技（常州）有限公司 | Preparation method of high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing composite layer |
| CN115850755B (en) * | 2022-12-14 | 2024-04-19 | 华中科技大学 | Microorganism modified lignin composite collagen film, preparation and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115895011A (en) * | 2022-10-25 | 2023-04-04 | 大连工业大学 | Preparation method of biodegradable black mulching film |
| CN115895011B (en) * | 2022-10-25 | 2023-09-12 | 大连工业大学 | Preparation method of biodegradable black mulching film |
| CN116041776A (en) * | 2022-11-01 | 2023-05-02 | 巴斯特医药科技（常州）有限公司 | Preparation method of high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing composite layer |
| CN115850755A (en) * | 2022-12-14 | 2023-03-28 | 华中科技大学 | Microbial modified lignin composite collagen film, preparation and application |
| CN115850755B (en) * | 2022-12-14 | 2024-04-19 | 华中科技大学 | Microorganism modified lignin composite collagen film, preparation and application |
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