CN115058899A - Preparation method of flame-retardant antibacterial degradable polylactic acid fiber membrane - Google Patents
Preparation method of flame-retardant antibacterial degradable polylactic acid fiber membrane Download PDFInfo
- Publication number
- CN115058899A CN115058899A CN202210440575.XA CN202210440575A CN115058899A CN 115058899 A CN115058899 A CN 115058899A CN 202210440575 A CN202210440575 A CN 202210440575A CN 115058899 A CN115058899 A CN 115058899A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- flame
- retardant
- temperature
- antibacterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 105
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 105
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 46
- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 239000012528 membrane Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920001661 Chitosan Polymers 0.000 claims abstract description 33
- 230000002195 synergetic effect Effects 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 10
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 13
- 229920000877 Melamine resin Polymers 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001963 growth medium Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229920006238 degradable plastic Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 241000222122 Candida albicans Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 229940095731 candida albicans Drugs 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 210000003470 mitochondria Anatomy 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002068 genetic effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 108010052285 Membrane Proteins Proteins 0.000 description 1
- 102000018697 Membrane Proteins Human genes 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 238000010545 Norrish reaction Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical group OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Manufacturing & Machinery (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant antibacterial degradable polylactic acid fiber membrane which is prepared from the following raw materials in parts by weight: 80-99.5 parts of polylactic acid, 0.5-20 parts of nitrogen and phosphorus synergistic chitosan grafted polylactic acid flame retardant and 4-20 parts of AG-12 antibacterial agent; the invention also discloses a preparation method of the flame-retardant antibacterial degradable polylactic acid fiber membrane. According to the invention, polylactic acid is taken as a matrix, nitrogen and phosphorus synergistic chitosan is used as an auxiliary material to graft the polylactic acid flame retardant and the AG-12 antibacterial agent, all raw materials can be degraded, or the raw materials are harmless to the environment after entering the environment, and the prepared flame-retardant antibacterial degradable polylactic acid fiber film has certain mechanical properties, meets the requirements of the mechanical properties, has certain antibacterial and flame-retardant capabilities, and is a degradable high polymer film with excellent comprehensive properties.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly provides a preparation method of a flame-retardant antibacterial degradable polylactic acid fiber film.
Background
The demand for plastics has continued to increase worldwide over the last several decades. However, waste plastic products of non-degradable plastics such as polystyrene, polypropylene, polyvinyl chloride, etc. are constantly flowing into the environment, becoming a white stain that is difficult to handle. Under the circumstances, the production and popularization of degradable materials become a good research topic, and the trend of replacing the traditional non-degradable plastics with green degradable plastics represented by polylactic acid is more and more obvious. With more and more newly-increased houses, the curtain is used as a necessary ornament of the house, the using amount is larger and larger, the traditional curtain only having the sun-shading function is more and more difficult to meet the market requirement, if the curtain is prepared by taking non-degradable plastics as raw materials, the white pollution is inevitably further worsened, and the research and development of the degradable curtain is increasingly urgent.
Disclosure of Invention
The invention aims to provide a preparation method of a novel flame-retardant antibacterial degradable polylactic acid fiber film, so as to prepare a curtain which can be used for a certain period and can be degraded after being discarded. The invention uses the centrifugal melt electrostatic spinning device in patent 202210048569X, takes polylactic acid as a polymer matrix, and is assisted with nitrogen and phosphorus synergistic chitosan in patent 202110515525.9 to graft a polylactic acid flame retardant and an AG-12 antibacterial agent. The prepared flame-retardant antibacterial degradable polylactic acid fiber film is uniform and thorough in degradation, free of residue and secondary pollution, has mechanical properties required by normal use, has certain antibacterial capability and flame retardant capability, and is a polymer fiber film with excellent comprehensive performance.
The technical scheme of the invention is as follows:
(1) placing the polylactic acid and nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant in a vacuum oven, vacuum-drying for 48 hours at 80 ℃, drying water, and uniformly mixing, wherein the preferable mixing proportion of the polylactic acid and the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant is 1 part of nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant and 99 parts of polylactic acid;
(2) starting and preheating a centrifugal melt electrostatic spinning device, setting the temperature of a screw extruder, the temperature of a feed delivery pipe heating sleeve and the temperature of a centrifugal throwing disk, setting the rotating speed of the centrifugal throwing disk, waiting for the temperature to be stable, and keeping the temperature for 1 hour, wherein the preferred scheme is that the temperature of the screw extruder is 200 ℃, the temperature of the feed delivery pipe heating sleeve is 220 ℃, the temperature of the centrifugal throwing disk is 260 ℃, and the rotating speed of the centrifugal throwing disk is 896 RPM;
(3) adding raw materials with different proportions into equipment, and carrying out centrifugal melt electrostatic spinning;
(4) respectively taking different amounts of the stock solutions of the antibacterial solution, adding ethanol for dilution to prepare the antibacterial solution, and preferably selecting the stock solutions of the antibacterial solution in volume ratio: ethanol ═ 40: 60, adding a solvent to the mixture;
(5) and (3) soaking the flame-retardant modified polylactic acid fiber membrane doped with the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant in an antibacterial solution, taking out after a certain time to prepare the flame-retardant antibacterial degradable polylactic acid fiber membrane, wherein the soaking time is preferably 7 days.
The invention has the beneficial effects that:
according to the invention, a nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant is added into a polylactic acid raw material of the flame-retardant antibacterial degradable polylactic acid fiber film to modify the polylactic acid raw material, so that the flame-retardant antibacterial degradable polylactic acid fiber film is prepared while the degradation capability of polylactic acid is not influenced. The polylactic acid group in the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant can interact with the polylactic acid base material to form a hydrogen bond, and the hydrogen bond is combined with the polylactic acid molecular chain, so that the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant is prevented from being separated out, the mobility of the molecular chain is increased, the viscosity of the polylactic acid melt is reduced, and the flame retardant effect is achieved. After heating, melamine is decomposed and polymerized, nitrogen-containing non-combustible gas such as nitrogen and oxynitride is partially generated, partial deamination condensation is performed, and melamine gradually reacts into melamine, melam and melem along with the evaporation of melamine. The generated nitrogen-containing gas can block oxygen, melamine and melam covering the surface of a combustion object absorb heat while evaporating, the combustion object is further prevented from contacting with the oxygen, the temperature is reduced, phosphate groups absorb the heat while burning, moisture generated by burning is absorbed, and the decomposed phosphoric acid, pyrophosphoric acid and even metaphosphoric acid also cover the surface of the polymer and promote carbon formation; meanwhile, melamine polyphosphate which is used as a branched chain melamine phosphate group can also generate melamine polyphosphate, and the melamine polyphosphate generated by the degradation of the flame-retardant modified chitosan can inhibit the evaporation of melamine and promote the condensation of the melamine. The chitosan as the main chain can also provide sufficient carbon source to assist carbon formation, and further improve the flame retardant property. Therefore, promoting carbonization at low temperatures can enhance the thermal stability and flame retardancy of the flame retardant material substrate. The flame-retardant modified chitosan can begin to degrade at low temperature, and volatile products of the flame-retardant modified chitosan appear earlier, so that a carbon layer can be formed more quickly, and a barrier effect is achieved. The flame retardant modified chitosan promotes the formation of carbon used as a physical protective barrier, thereby inhibiting the transfer of substances, blocking the contact of oxygen with the combustion point, and thus reducing the number of flammable volatiles such as carbonyl compounds and aldehydes. In addition, after the flame-retardant modified chitosan is added, the amount of released carbon dioxide can be greatly increased. Carbon dioxide is non-flammable and dilutes the concentration of flammable products and oxygen, thereby preventing combustion of the material.
Furthermore, the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant is added into the polylactic acid raw material of the flame-retardant antibacterial degradable polylactic acid fiber membrane to modify the polylactic acid raw material, so that the flame-retardant antibacterial degradable polylactic acid fiber membrane is prepared, and the flowability of the polylactic acid melt is improved while the flame-retardant capability is provided for the fiber membrane. The polylactic acid molecules have strong polarity, the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant not only comprises phosphate groups with strong polarity and polylactic acid groups compatible with a polylactic acid base material, but also comprises melamine groups with poor compatibility and poor polarity compared with polylactic acid, and after the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant is added into a polylactic acid melt, the polylactic acid groups in the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant can be combined with the molecules in the polylactic acid base material to form hydrogen bonds. The melamine and the chitosan on the same molecular chain have weaker polarity, the bonding capacity with the polylactic acid molecular chain is lower than that of the polylactic acid and the polylactic acid, the melamine and the chitosan are clamped between the polylactic acid molecular chains, the attraction between the polylactic acid molecular chains is greatly reduced, the moving resistance of the chain segments is smaller, the mobility of the polylactic acid molecular chains is increased, and the entanglement between the polylactic acid molecular chains is reduced, fig. 1 is a line chart of influence of different nitrogen and phosphorus synergistic chitosan grafted polylactic acid flame retardant addition amounts on the diameter of the flame-retardant antibacterial degradable polylactic acid fiber film, and fig. 2 is an electron microscope chart of the diameter of the flame-retardant antibacterial degradable polylactic acid fiber film after the chitosan nitrogen and phosphorus synergistic grafted polylactic acid flame retardant with different contents is added.
After the preparation of the flame-retardant modified polylactic acid fiber membrane is finished, the fiber membrane is subjected to post-treatment by using silver-containing antibacterial solution to prepare the flame-retardant antibacterial degradable polylactic acid fiber membrane. The antibacterial action is mainly divided into four mechanisms, wherein silver is combined with membrane protein to cause the cell membrane of bacteria or fungi to be damaged, and cytoplasm and cell structures in cells are lost to cause cell death; secondly, part of silver can enter the cell and is combined with genetic materials of bacteria or fungi, so that the synthesis of cell materials is blocked, and the sequencing of genetic factors is damaged; thirdly, silver entering the cell interior also destroys the mitochondria of the cell and reacts with chemical bonds in proteins or other cellular materials, for example silver reacts with sulfhydryl groups to destroy protein structure; fourthly, the damaged mitochondria and proteins jointly generate a large amount of active oxygen which cannot be decomposed by cells and is toxic to the cells, and cell substances such as the damaged mitochondria and proteins cannot be supplemented due to the damage of genetic factors, so that the death of the cells is further accelerated.
According to the invention, polylactic acid is used as a base material, and the degradable capability of the flame-retardant antibacterial degradable polylactic acid fiber membrane is endowed. The polylactic acid is cracked by a Norrish reaction mechanism under ultraviolet irradiation, and has two decomposition modes, firstly, carbon-oxygen single bonds in carboxyl groups are cracked by the ultraviolet irradiation to form acyl free radicals and alkyl free radicals, molecular chains are cracked, the two free radicals can further react to generate carboxyl and hydroxyl, the carboxyl in the polymer cannot be removed, the decomposition of the polymer is further accelerated, and the polymer is degraded from inside to outside. Secondly, under the condition of light excitation, a ring can be formed between a carbonyl group in a polylactic acid molecular chain and an adjacent ethylene group, a hydrogen atom on a vinylidene group is abstracted by carbonyl oxygen in an excited state to form a diradical, then, C-O bond breakage occurs between an ester group and the ethylene group, and further oxidation is performed to form carboxylic acid and unsaturated polyester (to form the vinylidene group), so that the molecular chain breakage is caused, and the relative molecular weight of the polymer is reduced. Using an ultraviolet light intensity of 90W/m 2 Is irradiated by an ultraviolet lamp with an intensity of aboutThe ultraviolet ray intensity of the sunlight is 90000 times, and the ultraviolet ray energy received by the fiber per hour is equal to the sum of the ultraviolet ray energy received by the fiber for 20 years calculated by daily illumination for 12 hours. In addition, the degradation of polylactic acid under natural conditions is also complexly influenced by various factors such as temperature, moisture, stress state, microorganism content and the like, and the corresponding relation between the polylactic acid and the ultraviolet irradiation time cannot be simply deduced here, and only the change of the degradation performance of the polylactic acid under strong ultraviolet irradiation is expressed. Fig. 3 is a graph of tensile strength and elongation at break of the flame-retardant antibacterial degradable polylactic acid fiber film irradiated by the ultraviolet lamp at different time and a photo of the flame-retardant antibacterial degradable polylactic acid fiber film after degradation. It can be seen from the figure that the flame-retardant antibacterial degradable polylactic acid fiber film without being irradiated by ultraviolet light has high tensile strength and elongation at break, and the mechanical strength is reduced after being irradiated by ultraviolet light, because the flame-retardant antibacterial degradable polylactic acid fiber film after being irradiated by ultraviolet light for 12 hours has too low strength, becomes brittle and can not be measured, and the flame-retardant antibacterial degradable polylactic acid fiber film after being irradiated by ultraviolet light for 15 hours has reduced strength until the strength can not maintain the self-weight, although the whole appearance can be maintained, the mechanical strength can not be measured, the flame-retardant antibacterial degradable polylactic acid fiber film after being irradiated for 24 hours is softened, is adhered to the surface of a culture dish and can not be taken out under the condition of maintaining the appearance, so the data curve only shows the mechanical strength without being irradiated by ultraviolet light and after being irradiated by ultraviolet light for 3, 6 and 9 hours, and proves that the flame-retardant polylactic acid fiber can be really extended along with the irradiation time of ultraviolet light, molecular chains are broken, the molecular chains of polylactic acid are broken due to ultraviolet rays for analysis reasons, the molecular weight of the polylactic acid is reduced, and the mechanical property of the polylactic acid fiber is reduced.
Drawings
FIG. 1 is a line graph showing the influence of different nitrogen and phosphorus synergistic chitosan grafted polylactic acid flame retardant addition amounts on the fiber diameters of flame-retardant, antibacterial and degradable polylactic acid fiber membranes.
Fig. 2 is an electron microscope image of the flame-retardant, antibacterial and degradable polylactic acid fiber membrane with different nitrogen and phosphorus synergistic chitosan grafted polylactic acid flame retardant content, wherein a, b, c, d and e are respectively the additive amount of nitrogen and phosphorus synergistic chitosan grafted polylactic acid flame retardant of 0.5%, 1%, 1.5%, 2% and 2.5%.
FIG. 3 is a photograph of a flame-retardant antibacterial degradable polylactic acid fiber membrane under different degradation times, a-f are photographs after ultraviolet irradiation for 3h, 6h, 9h, 12h, 15h and 24h respectively, g is a tensile strength line graph, and h is a fracture elongation line graph.
FIG. 4 is a picture of the zone of inhibition of the flame retardant, antibacterial and degradable polylactic acid fiber membrane, wherein a and b are Candida albicans culture media, c and d are Staphylococcus aureus culture media, and e and f are Escherichia coli culture media.
Detailed Description
Examples
(1) 99g of polylactic acid and 1g of nitrogen and phosphorus synergistic chitosan grafted polylactic acid flame retardant are placed in a vacuum oven for vacuum drying for 48 hours at the temperature of 80 ℃, the moisture is dried, and the mixture is uniformly mixed to prepare a blend.
(2) Starting and preheating a centrifugal melt electrostatic spinning device, setting the temperature of a screw extruder to be 200 ℃ and 220 ℃, setting the temperature of a feed delivery pipe heating sleeve to be 220 ℃, setting a centrifugal throwing disc to be 260 ℃, setting the rotating speed of the centrifugal throwing disc to be 896RPM, waiting for the temperature to be stable, and keeping the temperature for 1 hour.
(3) Adding the blend into equipment, and performing centrifugal melt electrostatic spinning to obtain the flame-retardant modified polylactic acid fiber membrane with the porosity of 80.8 percent and the surface density of 0.013g/cm 2 And an oxygen index of 42.3.
(4) Preparing 50% concentration antibacterial solution, taking 20ml of antibacterial solution stock solution, adding 20ml of ethanol for dilution, and preparing the antibacterial solution.
(5) And (3) soaking the flame-retardant modified polylactic acid fiber membrane doped with the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant in an antibacterial agent, and taking out after 7 days to prepare the flame-retardant antibacterial degradable polylactic acid fiber membrane.
The antibacterial treatment parameters are shown in table 1, and the results of the zone experiments on staphylococcus aureus, candida albicans and escherichia coli are shown in fig. 4, wherein a and b are candida albicans culture media, c and d are staphylococcus aureus culture media, and e and f are escherichia coli culture media.
TABLE 1 antimicrobial treatment parameters
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (1)
1. A preparation method of a flame-retardant antibacterial degradable polylactic acid fiber membrane is characterized by comprising the following steps: the following preparation scheme is adopted:
(1) placing the polylactic acid and nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant in a vacuum oven, vacuum-drying for 48 hours at 80 ℃, drying water, and uniformly mixing, wherein the preferable mixing proportion of the polylactic acid and the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant is 1 part of nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant and 99 parts of polylactic acid;
(2) starting and preheating a centrifugal melt electrostatic spinning device, setting the temperature of a screw extruder, the temperature of a feed delivery pipe heating sleeve and the temperature of a centrifugal throwing disk, setting the rotating speed of the centrifugal throwing disk, waiting for the temperature to be stable, and keeping the temperature for 1 hour, wherein the preferred scheme is that the temperature of the screw extruder is 200 ℃, the temperature of the feed delivery pipe heating sleeve is 220 ℃, the temperature of the centrifugal throwing disk is 260 ℃, and the rotating speed of the centrifugal throwing disk is 896 RPM;
(3) adding raw materials with different proportions into equipment, and carrying out centrifugal melt electrostatic spinning;
(4) respectively taking different amounts of the stock solutions of the antibacterial solution, adding ethanol for dilution to prepare the antibacterial solution, and preferably selecting the stock solutions of the antibacterial solution in volume ratio: ethanol ═ 40: 60;
(5) and (3) soaking the flame-retardant modified polylactic acid fiber membrane doped with the nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant in an antibacterial solution, taking out after a certain time to prepare the flame-retardant antibacterial degradable polylactic acid fiber membrane, wherein the soaking time is preferably 7 days.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210440575.XA CN115058899A (en) | 2022-04-25 | 2022-04-25 | Preparation method of flame-retardant antibacterial degradable polylactic acid fiber membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210440575.XA CN115058899A (en) | 2022-04-25 | 2022-04-25 | Preparation method of flame-retardant antibacterial degradable polylactic acid fiber membrane |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115058899A true CN115058899A (en) | 2022-09-16 |
Family
ID=83196437
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210440575.XA Pending CN115058899A (en) | 2022-04-25 | 2022-04-25 | Preparation method of flame-retardant antibacterial degradable polylactic acid fiber membrane |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115058899A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006063473A (en) * | 2004-08-26 | 2006-03-09 | Sawada Menko:Kk | Biodegradable flame retardant nonwoven fabric and filter |
CN105200663A (en) * | 2015-11-04 | 2015-12-30 | 上海洁晟环保科技有限公司 | Preparation method of antibacterial nanofiber membrane |
CN109825952A (en) * | 2019-02-22 | 2019-05-31 | 天津工业大学 | A kind of polylactic acid degradable composite nonwoven material and its preparation method and application |
CN111286175A (en) * | 2020-03-16 | 2020-06-16 | 赵梓权 | Degradable spinning raw material, degradable fiber membrane and degradable protective cover |
CN113121809A (en) * | 2021-05-12 | 2021-07-16 | 温多利遮阳材料(德州)股份有限公司 | Nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant and preparation method thereof |
CN114351359A (en) * | 2022-01-17 | 2022-04-15 | 北京化工大学 | Integrated centrifugal electrostatic spinning equipment |
-
2022
- 2022-04-25 CN CN202210440575.XA patent/CN115058899A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006063473A (en) * | 2004-08-26 | 2006-03-09 | Sawada Menko:Kk | Biodegradable flame retardant nonwoven fabric and filter |
CN105200663A (en) * | 2015-11-04 | 2015-12-30 | 上海洁晟环保科技有限公司 | Preparation method of antibacterial nanofiber membrane |
CN109825952A (en) * | 2019-02-22 | 2019-05-31 | 天津工业大学 | A kind of polylactic acid degradable composite nonwoven material and its preparation method and application |
CN111286175A (en) * | 2020-03-16 | 2020-06-16 | 赵梓权 | Degradable spinning raw material, degradable fiber membrane and degradable protective cover |
CN113121809A (en) * | 2021-05-12 | 2021-07-16 | 温多利遮阳材料(德州)股份有限公司 | Nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant and preparation method thereof |
CN114351359A (en) * | 2022-01-17 | 2022-04-15 | 北京化工大学 | Integrated centrifugal electrostatic spinning equipment |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102372907B (en) | Halogen-free flame retarding and glass fiber reinforced resin and its preparation method | |
Singha et al. | Effects of plasticizer/cross-linker on the mechanical and thermal properties of starch/PVA blends | |
Wang et al. | Degradation and stabilization of poly (butylene adipate-co-terephthalate)/polyhydroxyalkanoate biodegradable mulch films under different aging tests | |
Ratanakamnuan et al. | Photobiodegradation of low‐density polyethylene/banana starch films | |
Xu et al. | Photo‐oxidation and biodegradation of polyethylene films containing polyethylene glycol modified TiO2 as pro‐oxidant additives | |
CN108659742B (en) | Degradable hot melt adhesive and preparation method thereof | |
CN113461950B (en) | Preparation method of green sustainable chemical-physical synergistic intumescent flame retardant system | |
CN112812368A (en) | Antibacterial flame-retardant material and application method thereof | |
CN115058899A (en) | Preparation method of flame-retardant antibacterial degradable polylactic acid fiber membrane | |
Camargo et al. | Evaluation of wet bacterial cellulose degradation in different environmental conditions | |
RU2656916C1 (en) | Method of obtaining thin films of tin-indium oxide | |
CN110128698B (en) | Environment-friendly flame-retardant smoke suppressant and preparation method thereof | |
CN110003630B (en) | Transparent wear-resistant flame-retardant antibacterial plastic and preparation method thereof | |
CN105196667B (en) | Medicinal flame retardant type plastic package material and its preparation technology | |
JP2003051215A (en) | Electric wire, signal wire and cable | |
CN114395221B (en) | Quaternary blending degradable intercalation antibacterial high-permeability preservative film and preparation method thereof | |
CN114085502A (en) | Flame-retardant antibacterial PET film and production process thereof | |
CN113265104B (en) | Polypropylene composite material and preparation method thereof | |
CN112500652B (en) | Anti-aging corrosion-resistant outdoor optical cable and preparation method thereof | |
CN114806023A (en) | Foaming material for floating equipment and preparation method thereof | |
Pokhrel et al. | Peanut Shells Cellulose Based Biodegradable Nanocomposites with Polyvinyl Pyrrolidone (PVP) and Polyvinyl Alcohol (PVA) | |
CN112538245A (en) | Daylighting tile resin and preparation method thereof | |
KR20150111822A (en) | An eco-friendly living vessel using biomass and a mehtod for producing the same | |
Asriza et al. | Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene | |
CN116144105B (en) | Preparation method of high-temperature-resistant biodegradable polypropylene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220916 |