CN116536791A - Modified graphene polylactic acid antibacterial fiber and preparation method and application thereof - Google Patents
Modified graphene polylactic acid antibacterial fiber and preparation method and application thereof Download PDFInfo
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- CN116536791A CN116536791A CN202310510566.8A CN202310510566A CN116536791A CN 116536791 A CN116536791 A CN 116536791A CN 202310510566 A CN202310510566 A CN 202310510566A CN 116536791 A CN116536791 A CN 116536791A
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- antibacterial
- graphene oxide
- polylactic acid
- halamine
- graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 212
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 138
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 137
- 239000000835 fiber Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 175
- 239000000463 material Substances 0.000 claims abstract description 75
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 239000004745 nonwoven fabric Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000007664 blowing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 9
- 238000002074 melt spinning Methods 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 8
- 230000001877 deodorizing effect Effects 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- KPDTTZWHFZUVCL-UHFFFAOYSA-N 1-prop-2-enylimidazolidine-2,4-dione Chemical compound C=CCN1CC(=O)NC1=O KPDTTZWHFZUVCL-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 claims description 3
- SGHHJMNTTHMRDX-UHFFFAOYSA-N 3-butan-2-yloxypropyl(trimethoxy)silane Chemical compound CCC(C)OCCC[Si](OC)(OC)OC SGHHJMNTTHMRDX-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- DOOIVRUWWSZANQ-UHFFFAOYSA-N 3-triphenylsilylpropane-1-thiol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CCCS)C1=CC=CC=C1 DOOIVRUWWSZANQ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002131 composite material Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- -1 guanidinium compound Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a modified graphene polylactic acid antibacterial fiber, a preparation method and application thereof, wherein polylactic acid is used as a fiber base material, and graphene oxide grafted N-halamine antibacterial material is uniformly loaded in the polylactic acid; the graphene oxide grafted N-halamine antibacterial material contains photosensitive sulfhydryl groups, and is combined with unsaturated bonds in polylactic acid through the photosensitive sulfhydryl groups. According to the invention, the graphene oxide is combined with the N-halamine precursor and the polylactic acid in a chemical bond manner by utilizing the silane coupling agent containing the photosensitive sulfhydryl group, so that the N-halamine is prevented from being separated from the graphene oxide grafted N-halamine antibacterial material and the graphene oxide grafted N-halamine antibacterial material is prevented from losing on the antibacterial fiber, the antibacterial effect of the prepared antibacterial fiber is stable, and the antibacterial timeliness is long. The antibacterial fiber obtained by the invention has good antibacterial property, antistatic property and strong mechanical property, and has great industrial and market application values.
Description
Technical Field
The invention relates to the technical field of antibacterial fabric preparation, in particular to a modified graphene polylactic acid antibacterial fiber, and a preparation method and application thereof.
Background
Various bacteria and viruses in the world are abused, so that great challenges are brought to human survival and social development, and medical filter products become main defense means for people against bacteria. Among products for filtering germs, the polylactic acid non-woven fabric has an important position, polylactic acid fibers and the non-woven fabric thereof can enable the surfaces of the products to form a weak acid environment, and have a certain mildew-proof effect and antibacterial effect, but the antibacterial effect of the pure polylactic acid fabric is not obvious, and germs adsorbed on the fibers still survive.
To solve the above problems, antibacterial modification of graphene-based polylactic acid fibers and nonwoven fabrics thereof has been widely studied in the past decades. The invention patent (application number is CN 202211052980.0) discloses a graphene-polylactic acid antibacterial master batch, a preparation method and application thereof, and an improved Hummers method is used for preparing a uniformly dispersed graphene oxide dispersion liquid; dissolving a guanidinium compound in water, adding the water into graphene oxide dispersion liquid, stirring, heating, winding guanidinium compound molecules on the surface of a graphene oxide two-dimensional lamellar structure through electrostatic interaction, and then carrying out suction filtration, washing and freeze drying to obtain a guanidinium-graphene assembly; and finally, carrying out melt blending, extrusion and granulation on the guanidine salt-graphene assembly and the polylactic acid base material to obtain the graphene-polylactic acid antibacterial master batch. However, in the scheme, the antibacterial guanidino compound molecules are assembled with graphene oxide only through electrostatic action, and the guanidinium-graphene assembly and the polylactic acid substrate are only physically melt-blended; in subsequent applications, the antibacterial material is prone to loss of antibacterial molecules or the entire guanidine salt-graphene assembly, and has poor antibacterial timeliness.
In the prior art, other methods for preparing the polylactic acid resistant fiber exist, such as combining an inorganic antibacterial agent, an organic antibacterial agent or a composite antibacterial agent with polylactic acid in the modes of surface grafting, surface coating, melt blending and the like, and can also carry out matrix modification on the polylactic acid and endow the polylactic acid with a polypropylene antibacterial group so as to improve the antibacterial property of the polylactic acid. However, the antibacterial polylactic acid fibers and the non-woven fabrics thereof prepared at present have the problems of more or less large dosage of antibacterial agents, easy loss of antibacterial components, short antibacterial time, high after-treatment cost, single function, serious environmental pollution and the like, and the research and development of safer, more efficient and less expensive antibacterial polylactic acid fibers are promoted.
In view of the above, there is a need to design an improved modified graphene polylactic acid antibacterial fiber, and a preparation method and application thereof, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide a modified graphene polylactic acid antibacterial fiber, a preparation method and application thereof, wherein graphene oxide is respectively combined with an N-halamine precursor and polylactic acid in a chemical bond mode by utilizing a silane coupling agent containing photosensitive sulfhydryl groups, so that loss of an N-halamine antibacterial material grafted by graphene oxide is avoided, antibacterial timeliness and mechanical strength of the modified graphene polylactic acid antibacterial fiber are improved, and the obtained antibacterial fiber has antibacterial performance, antistatic performance and strong mechanical performance and has great market application value.
In order to achieve the aim, the invention provides a modified graphene polylactic acid antibacterial fiber, which takes polylactic acid as a fiber base material, wherein graphene oxide grafted N-halamine antibacterial material is uniformly loaded in the polylactic acid; the graphene oxide grafted N-halamine antibacterial material contains photosensitive sulfhydryl groups, and the graphene oxide grafted N-halamine antibacterial material is combined with unsaturated bonds in the polylactic acid through the photosensitive sulfhydryl groups.
As a further improvement of the invention, the mass ratio of the polylactic acid to the graphene oxide grafted N-halamine antibacterial material is 1000 (3-15).
As a further improvement of the invention, in the step S2, the mass ratio of the lamellar graphene oxide to the mercaptosilane coupling agent is (7-10): 100.
The invention also provides a preparation method of the modified graphene polylactic acid antibacterial fiber, which comprises the following steps:
s1, dispersing graphene oxide in deionized water, and performing ultrasonic stripping to obtain graphene oxide colloid; adding an alkaline solution into the graphene oxide colloid, stirring at 95-100 ℃, and washing, filtering and drying after the reaction is finished to obtain lamellar graphene oxide;
s2, adding the lamellar graphene oxide obtained in the step S1 and a mercaptosilane coupling agent into absolute ethyl alcohol according to a proportion to prepare a mixed solution, adding an N-halamine precursor and a photoinitiator into the mixed solution, and carrying out centrifugation, washing and vacuum drying after illumination for 1.0-2.0 h to obtain graphene oxide grafted N-halamine antibacterial powder;
s3, mixing the graphene oxide grafted N-halamine antibacterial powder obtained in the step S2 with polylactic acid according to a preset proportion, and adding the mixture into a melt-blowing machine for melt-blowing treatment after illumination for 0.5-1.5 h to obtain a graphene oxide grafted N-halamine melt-blowing material;
s4, soaking the graphene oxide grafted N-halamine melt-blown material obtained in the step S3 in sodium hypochlorite for 0.5-1.0 h, and washing, drying and heat treating to obtain the graphene oxide grafted N-halamine antibacterial melt-blown material;
and S5, carrying out melt spinning on the graphene oxide grafted N-halamine antibacterial melt-blown material prepared in the step S4 to obtain the modified graphene polylactic acid antibacterial fiber.
As a further improvement of the invention, the mass ratio of the lamellar graphene oxide to the mercaptosilane coupling agent is (1-9) 100; the addition amount of the sulfhydryl silane coupling agent is 1-5% of the mass of the polylactic acid.
As a further improvement of the invention, in the step S2, the addition amount of the N-halamine precursor is 0.5% -1.5% of the mass of the lamellar graphene oxide, and the addition amount of the photoinitiator is 0.5% -5.0% of the mass of the lamellar graphene oxide.
As a further improvement of the invention, in the step S5, deodorizing particles are added to the graphene oxide grafted N-halamine antibacterial melt-blown material during the melt spinning, and the graphene oxide grafted N-halamine antibacterial melt-blown material participates in the melt spinning together to obtain a modified graphene polylactic acid antibacterial fiber with deodorizing function; the deodorizing particles comprise one or more of active carbon particles, nano silver particles and active oxygen particles.
As a further improvement of the present invention, in step S1, the graphene oxide preparation comprises the steps of:
SS1, adding a solid mixture of graphite powder and sodium nitrate into concentrated sulfuric acid in an ice water bath under magnetic stirring, slowly adding potassium perchlorate, simultaneously adding potassium permanganate in batches for reaction, and taking out after the reaction temperature is not more than 20 ℃ and 0.5-1.5 h;
SS2, stirring the solution treated by the step SS1 at room temperature for 24 hours, and using H with the mass fraction of 5 percent 2 SO 4 Diluting the solution, stirring for 0.5-1.0H, and adding H 2 O 2 Stirring and reacting for 0.5-2.0 h, and centrifuging to obtain a solid substance;
SS 3H for the solid matter obtained in step SS2 2 SO 4 、H 2 O 2 And respectively washing the mixed solution and the HCI solution for 1-3 times, and finally washing the mixed solution and the HCI solution for 1-3 times by using distilled water to ensure that the pH value of the mixed solution is 7, and drying to obtain a yellow brown precipitate, namely the graphene oxide.
As a further improvement of the present invention, in step S2, the mercaptosilane coupling agent includes one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethyloxysilane, 3-mercaptopropyl triphenylsilane, 3- (methylpropyloxy) propyl trimethoxysilane; the N-halamine precursor comprises one of methacrylamide, 1-allyl hydantoin and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine.
As a further improvement of the present invention, in step S2, the photoinitiator comprises one of benzoin dimethyl ether, isopropyl thioxanthone, triaryliodonium salt.
The invention also provides application of the modified graphene polylactic acid antibacterial fiber, wherein the modified graphene polylactic acid antibacterial fiber is prepared by any one of the above or the preparation method of any one of the above, the modified graphene polylactic acid antibacterial fiber is applied to preparation of antibacterial non-woven fabrics, and the antibacterial non-woven fabrics are used for preparation of one or more antibacterial protection products in medical masks, medical protective clothing and industrial clothing.
The beneficial effects of the invention are as follows:
1. according to the modified graphene polylactic acid antibacterial fiber provided by the invention, polylactic acid is taken as a fiber base material, and graphene oxide grafted N-halamine antibacterial material is uniformly loaded in the polylactic acid; the graphene oxide grafted N-halamine antibacterial material contains photosensitive sulfhydryl groups, and is combined with unsaturated bonds in polylactic acid through the photosensitive sulfhydryl groups. According to the invention, graphene oxide is combined with the N-halamine precursor and the polylactic acid in a chemical bond mode by utilizing the silane coupling agent containing the photosensitive sulfhydryl group, so that the loss of the graphene oxide grafted N-halamine antibacterial material is avoided, the antibacterial timeliness and the mechanical strength of the modified graphene polylactic acid antibacterial fiber are improved, and the obtained antibacterial fiber has antibacterial performance, antistatic performance and higher mechanical performance, and has great market application value.
2. The method comprises the steps of firstly combining an N-halamine precursor onto graphene oxide in a chemical bond mode, and simultaneously adding a silane coupling agent containing photosensitive sulfhydryl groups to prevent the loss of the N-halamine precursor; the coupling agent can react with graphene oxide, N-halamine precursor and polylactic acid, and under the condition of illumination, the N-halamine precursor reacts with active groups on the surface of the graphene oxide again through the silane coupling agent, and photosensitive sulfhydryl groups on the graphene oxide are combined with unsaturated bonds in the polylactic acid in a chemical bond mode; thereby avoiding the detachment of the N-halamine from the graphene oxide grafted N-halamine antibacterial material and the loss of the graphene oxide grafted N-halamine antibacterial material on the antibacterial fiber taking polylactic acid as the base material, and ensuring that the prepared antibacterial fiber or antibacterial non-woven fabric has good antibacterial effect and long antibacterial timeliness.
3. The graphene oxide with the lamellar structure has large specific surface area, a large number of active groups are contained on the surface, the grafting rate is high, the grafting rate of the graphene oxide is further improved by adding the sulfhydryl silane coupling agent, and more reaction sites are provided for N-halamine and the coupling agent containing photosensitive sulfhydryl groups; the existence of photosensitive sulfhydryl groups on the surface of the graphene oxide realizes the stable combination of the graphene oxide grafted N-halamine antibacterial material and polylactic acid resin in a short time, and improves the antibacterial performance of the prepared material and the loading fastness of the antibacterial material. In addition, the graphene oxide with a lamellar structure has good conductivity, and after being melt-blended with polylactic acid, the graphene oxide has an antistatic function; and the graphene oxide with lamellar structure has anisotropy in the fiber, so that the strength of the antibacterial fiber is improved, and the fiber has good comprehensive performance when being applied to antibacterial non-woven fabrics.
4. According to the invention, the graphene oxide is subjected to antibacterial modification and is endowed with photosensitive sulfhydryl groups, and the addition amount of the sulfhydryl silane coupling agent and the N-halamine precursor is limited, so that the loss of the N-halamine antibacterial agent is better avoided and the separation of the graphene oxide is prevented; meanwhile, the mass ratio of the graphene oxide grafted N-halamine antibacterial material to the polylactic acid is limited, the antibacterial performance is exerted to the maximum on the basis of saving the cost, and the method has industrial mass production value.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of the modified graphene polylactic acid antibacterial fiber.
FIG. 2 is a diagram showing the molecular structure change of the graphene oxide grafted N-halamine antibacterial powder prepared in example 1.
Fig. 3 is an electron microscopic view of the modified graphene polylactic acid antibacterial fiber prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The modified graphene polylactic acid antibacterial fiber takes polylactic acid as a fiber base material, and graphene oxide grafted N-halamine antibacterial material is uniformly loaded in the polylactic acid; the graphene oxide grafted N-halamine antibacterial material contains photosensitive sulfhydryl groups, and the graphene oxide grafted N-halamine antibacterial material is combined with unsaturated bonds in polylactic acid through the photosensitive sulfhydryl groups. Wherein the mass ratio of polylactic acid to graphene oxide grafted N-halamine antibacterial material is 1000 (3-15), and the mass ratio of lamellar graphene oxide to mercapto silane coupling agent is preferably (7-10): 100. According to the invention, graphene oxide is combined with the N-halamine precursor and the polylactic acid in a chemical bond mode by utilizing the silane coupling agent containing the photosensitive sulfhydryl group, so that the loss of the graphene oxide grafted N-halamine antibacterial material is avoided, the antibacterial timeliness and the mechanical strength of the modified graphene polylactic acid antibacterial fiber are improved, and the obtained antibacterial fiber and the antibacterial non-woven fabric have antibacterial performance, antistatic performance and strong mechanical performance, and have great market application value.
Referring to fig. 1, a preparation method of the modified graphene polylactic acid antibacterial fiber comprises the following steps:
s1, dispersing graphene oxide in deionized water, and performing ultrasonic stripping to obtain graphene oxide colloid; adding an alkaline solution into the graphene oxide colloid, stirring at 95-100 ℃, and washing, filtering and drying after the reaction is finished to obtain lamellar graphene oxide; wherein the ultrasonic power is 60W and the time is 2-4 h;
s2, adding the lamellar graphene oxide obtained in the step S1 and a mercapto silane coupling agent into absolute ethyl alcohol according to a proportion to prepare a mixed solution, adding an N-halamine precursor and a photoinitiator into the mixed solution, and carrying out centrifugation, washing and vacuum drying after illumination for 1.0-2.0 h to obtain graphene oxide grafted N-halamine antibacterial powder;
wherein the mass ratio of the lamellar graphene oxide to the mercaptosilane coupling agent is (1-9): 100, and the addition amount of the mercaptosilane coupling agent is 1% -5% of the mass of the polylactic acid; the addition amount of the N-halamine precursor is 0.5-1.5% of the mass of the lamellar graphene oxide, and the addition amount of the photoinitiator is 0.5-5.0% of the mass of the lamellar graphene oxide; according to the invention, the graphene oxide is subjected to antibacterial modification and is endowed with photosensitive sulfhydryl groups, and the addition amount of the sulfhydryl silane coupling agent and the N-halamine precursor is limited, so that the loss of the N-halamine antibacterial agent is better avoided and the separation of the graphene oxide is prevented; meanwhile, the mass ratio of the graphene oxide grafted N-halamine antibacterial material to the polylactic acid is limited, and the antibacterial performance is exerted to the maximum on the basis of saving the cost, so that the method has industrial mass production value;
s3, mixing the graphene oxide grafted N-halamine antibacterial powder obtained in the step S2 with polylactic acid according to a preset proportion, and adding the mixture into a melt-blowing machine for melt-blowing treatment after illumination for 0.5-1.5 h to obtain a graphene oxide grafted N-halamine melt-blowing material;
s4, soaking the graphene oxide grafted N-halamine melt-blown material obtained in the step S3 in sodium hypochlorite for 0.5-1.0 h, and washing, drying and heat treating to obtain the graphene oxide grafted N-halamine antibacterial melt-blown material; the graphene oxide grafted N-halamine melt-blown material is subjected to chlorination treatment, so that the regeneration of antibacterial performance can be realized;
and S5, carrying out melt spinning on the graphene oxide grafted N-halamine antibacterial melt-blown material prepared in the step S4 to obtain the modified graphene polylactic acid antibacterial fiber.
Specifically, the preparation method comprises the steps of firstly combining an N-halamine precursor onto graphene oxide in a chemical bond mode, and simultaneously adding a silane coupling agent containing photosensitive sulfhydryl groups to prevent the loss of the N-halamine precursor; the coupling agent can react with graphene oxide, N-halamine precursor and polylactic acid, and under the condition of illumination, the N-halamine precursor reacts with active groups on the surface of the graphene oxide again through the silane coupling agent, and photosensitive sulfhydryl groups on the graphene oxide are combined with unsaturated bonds in the polylactic acid in a chemical bond mode; thereby avoiding the detachment of the N-halamine from the graphene oxide grafted N-halamine antibacterial material and the loss of the graphene oxide grafted N-halamine antibacterial material on the antibacterial fiber, and ensuring that the prepared antibacterial fiber has good antibacterial effect and long antibacterial timeliness.
Specifically, in step S1, the graphene oxide modified Hummers method is prepared, including the steps of:
SS1, adding a solid mixture of graphite powder and sodium nitrate into concentrated sulfuric acid in an ice water bath under magnetic stirring, slowly adding potassium perchlorate, simultaneously adding potassium permanganate in batches for reaction, and taking out after the reaction temperature is not more than 20 ℃ and 0.5-1.5 h; the mass ratio of the potassium perchlorate to the potassium permanganate is 5:3;
SS2, stirring the solution treated by the step SS1 at room temperature for 24 hours, and using H with the mass fraction of 5 percent 2 SO 4 Diluting the solution, stirring for 0.5-1.0H, and adding H 2 O 2 Stirring and reacting for 0.5-2.0 h, and centrifuging to obtain a solid substance;
SS3, subjecting the solid matter obtained in step SS2 to H 2 SO 4 、H 2 O 2 And respectively washing the mixed solution and the HCI solution for 1-3 times, and finally washing the mixed solution and the HCI solution for 1-3 times by using distilled water to ensure that the pH value of the mixed solution is 7, and drying to obtain a yellow brown precipitate, namely the graphene oxide.
The graphene oxide with lamellar structure selected in the preparation method has large specific surface area, a large number of active groups are contained on the surface, the grafting rate is high, the grafting rate of the graphene oxide is further improved by adding the sulfhydryl silane coupling agent, more reaction sites are provided for the N-halamine and the coupling agent containing photosensitive sulfhydryl groups, and the existence of the photosensitive sulfhydryl groups on the surface of the graphene oxide realizes the stable combination of the graphene oxide grafted N-halamine antibacterial material and the polylactic acid resin in a short time, and the antibacterial performance and antibacterial load fastness of the prepared material are improved. In addition, the graphene oxide with a lamellar structure has good conductivity, and after being melt-blended with polylactic acid, the graphene oxide has an antistatic function; and the graphene oxide with lamellar structure has anisotropy in the fiber, so that the strength of the antibacterial fiber is improved, and the antibacterial fiber has good comprehensive performance.
In step S2, the mercaptosilane coupling agent comprises one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethyloxysilane, 3-mercaptopropyl triphenylsilane, 3- (methylpropyloxy) propyl trimethoxysilane; the N-halamine precursor comprises one of methacrylamide, 1-allyl hydantoin and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine; the photoinitiator comprises one of benzoin dimethyl ether, isopropyl thioxanthone and triaryliodonium salt.
In some specific embodiments, in step S5, when the graphene oxide grafted N-halamine antibacterial melt-blown material is melt-spun, deodorant particles are added to the graphene oxide grafted N-halamine antibacterial melt-blown material to participate in the melt-spinning together, so as to obtain a modified graphene polylactic acid antibacterial fiber with a deodorant function; the deodorizing particles comprise one or more of activated carbon particles, nano silver particles and activated oxygen particles.
In some specific embodiments, in step S1, the alkaline solution is a sodium hydroxide solution.
The application of the modified graphene polylactic acid antibacterial fiber is that the modified graphene polylactic acid antibacterial fiber is applied to the preparation of antibacterial non-woven fabrics, and the antibacterial non-woven fabrics are used for preparing one or more antibacterial protection products in medical masks, medical protective clothing and industrial clothing.
Example 1
The embodiment provides a preparation method of a modified graphene polylactic acid antibacterial fiber, which comprises the following steps:
s1, preparing lamellar graphene oxide by adopting an improved Hummers method;
s11, adding 2g of graphite powder and 1g of solid mixture of sodium nitrate into concentrated sulfuric acid in an ice-water bath under magnetic stirring, slowly adding 10g of potassium perchlorate, simultaneously adding 6g of potassium permanganate in batches for reaction, and taking out after the reaction temperature is not more than 20 ℃ and 1.5 h;
s12, stirring the solution processed in the step S11 at room temperature for reaction for 24 hours,and H with mass fraction of 5% 2 SO 4 The solution was diluted and stirred for 1H, then 6mL of H was added 2 O 2 The solution turns into bright yellow, and is stirred for 2h for reaction and centrifugated to obtain a solid substance;
s13, using H for the solid material obtained in the step S12 2 SO 4 、H 2 O 2 And (3) respectively washing the mixed solution and the HCI solution for 2 times, and finally washing the mixed solution and the HCI solution with distilled water for 3 times to ensure that the pH value of the mixed solution is 7, and fully drying the mixed solution and the HCI solution in a vacuum drying oven at 40 ℃ to obtain a yellow brown precipitate, namely Graphene Oxide (GO).
S14, dispersing graphene oxide in deionized water, and performing ultrasonic stripping for 3 hours at a power of 60W to obtain graphene oxide colloid; adding an alkaline solution into the graphene oxide colloid, stirring at 95 ℃, washing, filtering, and drying at 40 ℃ in an oven after the reaction is finished to obtain lamellar graphene oxide;
s2, adding lamellar graphene oxide obtained in the step S1 and 3-mercaptopropyl trimethoxy silane into absolute ethyl alcohol according to a mass ratio of 5:100 to prepare a mixed solution, adding methacrylamide and a photoinitiator benzoin dimethyl ether into the mixed solution, and carrying out centrifugation, washing and vacuum drying after 1h of illumination to obtain graphene oxide grafted N-halamine antibacterial powder; the addition amount of the methacrylamide is 1% of the mass of the lamellar graphene oxide, the addition amount of the photoinitiator is 0.5% of the mass of the lamellar graphene oxide, and the addition amount of the 3-mercaptopropyl trimethoxysilane is 3% of the mass of the polylactic acid;
s3, mixing the graphene oxide grafted N-halamine antibacterial powder obtained in the step S2 with polylactic acid (PLA) according to the mass ratio of 9:1000, and adding the mixture into a melt-blowing machine for melt-blowing treatment after illumination for 1h to obtain a graphene oxide grafted N-halamine melt-blowing material;
s4, soaking the graphene oxide grafted N-halamine melt-blown material obtained in the step S3 in sodium hypochlorite for 30min, and washing, drying and heat treating to obtain the graphene oxide grafted N-halamine antibacterial melt-blown material;
and S5, carrying out melt spinning on the graphene oxide grafted N-halamine antibacterial melt-blown material prepared in the step S4 to obtain the modified graphene polylactic acid antibacterial fiber.
Referring to fig. 2, a process diagram of the molecular structure change of the graphene oxide grafted N-halamine antibacterial powder prepared in this embodiment is shown. The graph shows that the molecular structure change process of the graphene oxide grafted N-halamine antibacterial powder is shown as follows, wherein the first step is that graphene oxide reacts with a mercaptosilane coupling agent to generate a graphene oxide-silane coupling agent compound containing a reaction functional group; in the second step, the graphene oxide-mercaptosilane coupling agent compound reacts with N-halamine through nucleophilic substitution reaction to form a graphene oxide grafted N-halamine compound.
Referring to fig. 3, an electron microscope image of the modified graphene polylactic acid antibacterial fiber prepared in example 1 is shown. From the figure, it can be seen that the protrusions on the surface of the polylactic acid-graphene oxide composite fiber can indicate that graphene oxide is mixed into polylactic acid, and the protrusion structures are formed by the dispersion and aggregation of graphene on the fiber surface. In the fiber preparation process, graphene oxide is often treated together with polylactic acid, and a mixture is formed for fiberization through steps of heating, extrusion and the like; in the process, graphene interacts with polylactic acid molecules and possibly gathers on the surface of the fiber to form protrusions, and the structure can effectively enhance the physical combination of the graphene and the polylactic acid, so that the performance of the composite material is improved. Therefore, the convex structure can be used for representing the composite condition of graphene and polylactic acid.
Examples 2 to 4
The embodiments 2 to 4 provide a preparation method of modified graphene polylactic acid antibacterial fibers, which is different from the embodiment 1 in that the mass ratio of graphene oxide grafted N-halamine antibacterial powder to polylactic acid in the embodiments 2 to 4 is 3:1000, 6:1000 and 12:1000 respectively; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Comparative example 1
Comparative example 1 provides a preparation method of a modified graphene polylactic acid antibacterial fiber, which is different from example 1 in that 3-mercaptopropyl trimethoxysilane and a photoinitiator are not added in step S2, and no light treatment is performed, and the rest is substantially the same as example 1, and is not repeated here.
Comparative examples 2 to 3
Comparative examples 2 to 3 provide a preparation method of modified graphene polylactic acid antibacterial fibers, and compared with example 1, the preparation method is different in that the mass ratio of graphene oxide grafted N-halamine antibacterial powder to polylactic acid in comparative examples 2 to 3 is 1:1000 and 20:1000 respectively; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Comparative example 4
Comparative example 4 provides a method for preparing a modified graphene polylactic acid antibacterial fiber, which is different from example 1 in that the chlorination treatment of step S4 is not performed; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Comparative example 5
Comparative example 5 provides a preparation method of a modified graphene polylactic acid antibacterial fiber, which is different from example 1 in that step S1 is not performed, and nano silica is used to replace lamellar graphene oxide in step S2; the remainder is substantially the same as that of example 1, and will not be described in detail here.
The antibacterial properties and mechanical properties of the modified graphene polylactic acid antibacterial fibers prepared in examples 1 to 4 and comparative examples 1 to 5 were measured, and the obtained results are shown in the following table.
Table 1 results of the antibacterial fiber property test of examples 1 to 4 and comparative examples 1 to 5
As can be seen from Table 1, the antibacterial fibers prepared by mixing polylactic acid with a certain mass of graphene oxide grafted N-halamine antibacterial powder have good antibacterial capability, and examples 1 to 4 and comparative examples 2 and 3 show that the antibacterial capability of the polylactic acid composite fiber has a tendency of rising and falling after the content of the graphene oxide grafted N-halamine antibacterial powder increases, which indicates that the addition amount of the graphene oxide grafted N-halamine antibacterial powder has a certain threshold value. In comparative example 1, the antibacterial ability of the fiber is lowered compared with that of the fiber without the mercaptosilane coupling agent, and the principle is that the graphene oxide grafted N-halamine antibacterial powder is agglomerated in the fiber to affect the antibacterial performance of the fiber, and when the mercaptosilane coupling agent is not added, the graphene oxide grafted N-halamine antibacterial material and the polylactic acid resin are not combined in chemical bond, so that the strength is affected, and the antibacterial performance loss is large after multiple chlorination. In comparative example 4, the non-chlorinated antibacterial ability of the fiber is reduced because the graphene oxide grafted N-halamine antibacterial powder needs to be chlorinated to activate its functional group to enhance the antibacterial ability of the composite fiber. In comparative example 5, the graphene oxide was changed to silica inorganic particles, and the antibacterial rate and strength were reduced because the inorganic particles were unevenly dispersed in the fiber and the antibacterial power was low in the adhesion to the resin matrix, so that the antibacterial ability was reduced. From the above, it is known that the addition of the mercapto silane coupling agent and the structure of the inorganic particles have an influence on the antibacterial performance and mechanical properties of the fiber according to the mass ratio of the graphene oxide grafted N-halamine antibacterial powder to the polylactic acid.
Examples 5 to 6
Embodiments 5 to 6 provide a preparation method of a modified graphene polylactic acid antibacterial fiber, which is different from embodiment 1 in that in embodiments 5 to 6, the addition amount of the mercaptosilane coupling agent is 1% and 5% of the mass of polylactic acid, and the rest is substantially the same as embodiment 1, and no description is repeated here.
Comparative examples 6 to 7
Comparative examples 6 to 7 provide a preparation method of modified graphene polylactic acid antibacterial fibers, which is different from example 1 in that the addition amount of the mercaptosilane coupling agent in examples 6 to 7 is 0.5% and 7% of the mass of polylactic acid, and the rest is substantially the same as example 1, and is not described here again.
Comparative examples 8 to 9
Comparative examples 8 to 9 provide a preparation method of modified graphene polylactic acid antibacterial fibers, and compared with example 1, the difference is that the addition amount of the N-halamine precursor in comparative examples 8 to 9 is 0.1% and 2% of the mass of lamellar graphene oxide, and the rest is substantially the same as example 1, and is not described here again.
The antibacterial properties and mechanical properties of the modified graphene polylactic acid antibacterial fibers prepared in examples 5 to 6 and comparative examples 6 to 9 were measured, and the obtained results are shown in the following table.
Table 2 results of the antibacterial fiber property test of examples 5 to 6 and comparative examples 6 to 9
| Antibacterial efficiency (%) | Antibacterial ratio after 20 times of chlorination (%) | Tensile Strength (MPa) | |
| Example 5 | 99.9 | 95.6 | 58 |
| Example 6 | 99.9 | 99.5 | 63 |
| Comparative example 6 | 99.9 | 94.8 | 56 |
| Comparative example 7 | 99.9 | 99.6 | 58 |
| Comparative example 8 | 96.7 | 95.4 | 56 |
| Comparative example 9 | 99.9 | 98.8 | 60 |
As can be seen from table 2, in general, doping with an appropriate amount of N-halamine precursor can increase the tensile strength of the polylactic acid composite material, but the degree of increase in tensile strength does not have a linear relationship with the content of N-halamine precursor, but follows a certain saturation trend. When the doping amount is lower than a certain range, the tensile strength of the polylactic acid composite material is firstly increased and then reduced along with the increase of the content of the N-halamine precursor. The sulfhydryl silane coupling agent can be used for improving the bonding strength between polylactic acid and graphene oxide, so that the mechanical property and durability of the material are improved; the addition amount of the sulfhydryl silane coupling agent in the polylactic acid can influence the tensile strength of the polylactic acid; the dosage of the sulfhydryl silane coupling agent is within the range of 1-5% of the mass of the polylactic acid, so that the tensile strength of the material can be obviously improved, and the mechanical property of the material is more excellent. The proper addition of the sulfhydryl silane coupling agent can obviously improve the combination effect of the polylactic acid and the graphene oxide, thereby improving the mechanical property and durability of the polylactic acid material, further improving the tensile strength of the polylactic acid, and having very important significance for the application of the polylactic acid material.
In summary, the invention provides a modified graphene polylactic acid antibacterial fiber, a preparation method and application thereof, wherein polylactic acid is used as a fiber base material, and graphene oxide grafted N-halamine antibacterial material is uniformly loaded in the polylactic acid; the graphene oxide grafted N-halamine antibacterial material contains photosensitive sulfhydryl groups, and is combined with unsaturated bonds in polylactic acid through the photosensitive sulfhydryl groups. In the preparation method, the graphene oxide is respectively combined with the N-halamine precursor and the polylactic acid in a chemical bond mode by utilizing the silane coupling agent containing the photosensitive sulfhydryl group, so that the detachment of the N-halamine from the graphene oxide grafted N-halamine antibacterial material and the loss of the graphene oxide grafted N-halamine antibacterial material on the antibacterial fiber are avoided, and the prepared antibacterial fiber has good antibacterial effect and long antibacterial timeliness. In addition, the selected lamellar graphene oxide provides more reaction sites, so that stable combination of the graphene oxide grafted N-halamine antibacterial material and polylactic acid resin in a short time is realized; the conductive polymer also has good conductivity, and endows the conductive polymer with antistatic function after being melt-blended with polylactic acid; the graphene oxide with the lamellar structure has anisotropy in the fiber, so that the strength of the antibacterial fiber is improved, and the comprehensive performance of the antibacterial fiber is good when the graphene oxide is applied to the preparation of antibacterial non-woven fabrics; the antibacterial fiber and the antibacterial non-woven fabric obtained by the invention have antibacterial performance, antistatic performance and strong mechanical performance, and have great market application value.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The modified graphene polylactic acid antibacterial fiber is characterized in that polylactic acid is used as a fiber base material, and graphene oxide grafted N-halamine antibacterial material is uniformly loaded in the polylactic acid; the graphene oxide grafted N-halamine antibacterial material contains photosensitive sulfhydryl groups, and the graphene oxide grafted N-halamine antibacterial material is combined with unsaturated bonds in the polylactic acid through the photosensitive sulfhydryl groups.
2. The modified graphene polylactic acid antibacterial fiber according to claim 1, wherein the mass ratio of polylactic acid to graphene oxide grafted N-halamine antibacterial material is 1000 (3-15).
3. A method for preparing the modified graphene polylactic acid antibacterial fiber according to claim 1 or 2, which is characterized by comprising the following steps:
s1, dispersing graphene oxide in deionized water, and performing ultrasonic stripping to obtain graphene oxide colloid; adding an alkaline solution into the graphene oxide colloid, stirring at 95-100 ℃, and washing, filtering and drying after the reaction is finished to obtain lamellar graphene oxide;
s2, adding the lamellar graphene oxide obtained in the step S1 and a mercaptosilane coupling agent into absolute ethyl alcohol according to a proportion to prepare a mixed solution, adding an N-halamine precursor and a photoinitiator into the mixed solution, and carrying out centrifugation, washing and vacuum drying after illumination for 1.0-2.0 h to obtain graphene oxide grafted N-halamine antibacterial powder;
s3, mixing the graphene oxide grafted N-halamine antibacterial powder obtained in the step S2 with polylactic acid according to a preset proportion, and adding the mixture into a melt-blowing machine for melt-blowing treatment after illumination for 0.5-1.5 h to obtain a graphene oxide grafted N-halamine melt-blowing material;
s4, soaking the graphene oxide grafted N-halamine melt-blown material obtained in the step S3 in sodium hypochlorite for 0.5-1.0 h, and washing, drying and heat treating to obtain the graphene oxide grafted N-halamine antibacterial melt-blown material;
and S5, carrying out melt spinning on the graphene oxide grafted N-halamine antibacterial melt-blown material prepared in the step S4 to obtain the modified graphene polylactic acid antibacterial fiber.
4. The method for preparing the modified graphene polylactic acid antibacterial fiber according to claim 3, wherein the mass ratio of the lamellar graphene oxide to the mercaptosilane coupling agent is (1-9) 100; the addition amount of the sulfhydryl silane coupling agent is 1-5% of the mass of the polylactic acid.
5. The method for preparing the modified graphene polylactic acid antibacterial fiber according to claim 3, wherein in the step S2, the addition amount of the N-halamine precursor is 0.5-1.5% of the mass of the lamellar graphene oxide, and the addition amount of the photoinitiator is 0.5-5.0% of the mass of the lamellar graphene oxide.
6. The method for preparing the modified graphene polylactic acid antibacterial fiber according to claim 3, wherein in the step S5, deodorizing particles are added into the graphene oxide grafted N-halamine antibacterial melt-blown material during the melt spinning, and the graphene oxide grafted N-halamine antibacterial melt-blown material and the deodorizing particles participate in the melt spinning together to obtain the modified graphene polylactic acid antibacterial fiber with a deodorizing function; the deodorizing particles comprise one or more of active carbon particles, nano silver particles and active oxygen particles.
7. The method for preparing the modified graphene polylactic acid antibacterial fiber according to claim 3, wherein in the step S1, the graphene oxide preparation comprises the following steps:
SS1, adding a solid mixture of graphite powder and sodium nitrate into concentrated sulfuric acid in an ice water bath under magnetic stirring, slowly adding potassium perchlorate, simultaneously adding potassium permanganate in batches for reaction, and taking out after the reaction temperature is not more than 20 ℃ and 0.5-1.5 h;
SS2, stirring the solution treated by the step SS1 at room temperature for 24 hours, and using H with the mass fraction of 5 percent 2 SO 4 Diluting the solution, stirring for 0.5-1.0H, and adding H 2 O 2 Stirring and reacting for 0.5-2.0 h, and centrifuging to obtain a solid substance;
SS 3H for the solid matter obtained in step SS2 2 SO 4 、H 2 O 2 And respectively washing the mixed solution and the HCI solution for 1-3 times, and finally washing the mixed solution and the HCI solution for 1-3 times by using distilled water to ensure that the pH value of the mixed solution is 7, and drying to obtain a yellow brown precipitate, namely the graphene oxide.
8. The method for preparing the modified graphene polylactic acid antibacterial fiber according to claim 3, wherein in the step S2, the mercaptosilane coupling agent comprises one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethyloxysilane, 3-mercaptopropyl triphenylsilane, 3- (methylpropyloxy) propyl trimethoxysilane; the N-halamine precursor comprises one of methacrylamide, 1-allyl hydantoin and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine.
9. The method for preparing a modified graphene polylactic acid antibacterial fiber according to claim 3, wherein in the step S2, the photoinitiator comprises one of benzoin dimethyl ether, isopropyl thioxanthone and triaryl iodonium salt.
10. The application of the modified graphene polylactic acid antibacterial fiber is characterized in that the modified graphene polylactic acid antibacterial fiber is prepared by the preparation method of any one of claims 1-2 or any one of claims 3-9, and the modified graphene polylactic acid antibacterial fiber is applied to the preparation of antibacterial non-woven fabrics, and the antibacterial non-woven fabrics are used for preparing one or more antibacterial protection products in medical masks, medical protective clothing and industrial clothing.
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