CN109183398B - 一种具有抗菌、疏水性的可降解膜及其制备方法 - Google Patents
一种具有抗菌、疏水性的可降解膜及其制备方法 Download PDFInfo
- Publication number
- CN109183398B CN109183398B CN201810927103.0A CN201810927103A CN109183398B CN 109183398 B CN109183398 B CN 109183398B CN 201810927103 A CN201810927103 A CN 201810927103A CN 109183398 B CN109183398 B CN 109183398B
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- nano core
- hydrophobic
- shell
- shell composite
- 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.)
- Active
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000011246 composite particle Substances 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims abstract description 13
- GHMPDSQDVBUXGI-UHFFFAOYSA-N 5,5-dimethyl-3-(3-triethoxysilylpropyl)imidazolidine-2,4-dione Chemical compound CCO[Si](OCC)(OCC)CCCN1C(=O)NC(C)(C)C1=O GHMPDSQDVBUXGI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 7
- RBVUMCHMXYUHAP-UHFFFAOYSA-N 5,5-dimethylimidazolidine-2,4-dione;sodium Chemical compound [Na].CC1(C)NC(=O)NC1=O RBVUMCHMXYUHAP-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 7
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 7
- 238000010041 electrostatic spinning Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 241001333951 Escherichia coli O157 Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241001646719 Escherichia coli O157:H7 Species 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- AFUWHLXUBJOPNO-UHFFFAOYSA-N CCCCCCCCCCCCCCCC[SiH3] Chemical compound CCCCCCCCCCCCCCCC[SiH3] AFUWHLXUBJOPNO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Chemical group 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004283 biguanides Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- 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
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
- D06B3/18—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics combined with squeezing, e.g. in padding machines
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种具有抗菌、疏水性的可降解膜及其制备方法，该方法包括如下步骤：(1)制得5,5‑二甲基海因钠盐；(2)制备5,5‑二甲基‑3‑(3'‑三乙氧基硅丙基)‑海因；(3)分离二氧化硅；(4)分离二氧化硅@二氧化钛纳米核壳颗粒；(5)分离具有抗菌无氟疏水的改性纳米核壳复合颗粒，再将所得改性纳米核壳复合颗粒配制整理液，浸染纤维膜，制成具有抗菌、疏水性的可降解膜。本发明用简单的方法制备了可控尺寸的纳米复合核壳颗粒，且可用来制备绿色可降解的抗菌疏水纤维膜。
Description
技术领域
本发明涉及可降解材料技术领域，尤其是涉及一种无氟、疏水、抗菌的纳米核壳颗粒的合成及其制备的抗菌疏水的纤维膜。
背景技术
据调查，2015年中国消耗了99.22亿个包装箱、169.85亿米的胶带及82.68 亿个塑料袋，这些快递大约会产生400多万吨的垃圾，胶带长度可绕地球425 圈，而这类材料大都化学稳定性较强，在自然环境下难以降解，这些垃圾需要上百年才能完全降解。此外，这些包装物难以处理，极易造成白色污染，滋养细菌等微生物。此外，日常生活存在着各种各样的微生物，其危害甚广。此外，一方面，微生物在温和的条件下容易引起材料的分解和腐败，造成经济方面的重大损失。另一方面，在医学领域方面，细菌感染已成为一个严峻的问题。
目前，常用的抗菌剂包括金属及其氧化物、季铵盐、季鏻盐、双胍类、壳聚糖及其衍生物等，但上述抗菌剂存在种种问题，如产生副产物，有的在自然界中不易降解，有的抗菌速率慢，杀菌效率低等。卤胺类抗菌剂是一种新型绿色有机抗菌剂，很大程度上弥补了上述缺陷，具有高效广谱杀菌、抗菌功能可再生和安全零污染等优点。另一方面，在疏水领域含氟疏水剂和长碳链硅烷疏水剂研究最为广泛。然而部分含氟化合物在使用中对自然友好性不好，会在生物体堆积有一定的危害，使其使用受限。相应的，硅氧烷类疏水剂使用更为普遍，也逐渐代替含氟类。
发明内容
针对现有技术存在的上述问题，本发明申请人提供了一种具有抗菌、疏水性的可降解膜及其制备方法。本发明用简单的方法制备了可控尺寸的纳米复合核壳颗粒，且可用来制备绿色可降解的抗菌疏水纤维膜。
本发明的技术方案如下：
一种具有抗菌、疏水性的纳米核壳复合颗粒，所述纳米核壳复合颗粒的制备方法包括如下步骤：
(1)将5,5-二甲基海因和氢氧化钠溶解于无水乙醇中并在90℃条件下搅拌反应10min，之后除去溶剂乙醇，真空干燥，制得5,5-二甲基海因钠盐；
(2)将步骤(1)制得的5,5-二甲基海因钠盐溶于N,N-二甲基甲酰胺中，加入γ-氯丙基三乙氧基硅烷，95℃冷凝回流反应8h，过滤、除溶剂，得到5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因；
(3)将四乙氧基硅烷加入氨水与乙醇的混合溶液中，并在60℃条件下反应 2h，之后离心分离出二氧化硅；
(4)将步骤(3)制得的二氧化硅分散在乙醇水溶液中，并加入乳化剂，分散均匀后将钛酸四丁酯滴加到混合溶液中，在50℃条件下反应8h，之后离心分离出二氧化硅@二氧化钛纳米核壳颗粒；
二氧化硅@二氧化钛纳米核壳材料为式(Ⅰ)所示结构的化合物：
(5)将步骤(4)制得的二氧化硅@二氧化钛纳米核壳颗粒在乙醇水溶液中超声分散均匀后，加入步骤(2)制得的5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因和十六烷基三乙氧基硅烷，室温下搅拌8h，之后离心分离出具有抗菌无氟疏水的改性纳米核壳复合颗粒。
步骤(1)中所述5,5-二甲基海因与氢氧化钠的摩尔比为1:1。
步骤(2)中所述5,5-二甲基海因钠盐与γ-氯丙基三乙氧基硅烷的摩尔比为1:1。
步骤(3)中所述氨水、水与乙醇的混合溶液中质量比为1:1:8，1:2:7，1:4:5 或1:6:3；所述氨水的质量浓度为28％。
步骤(4)中所述乳化剂为烷基酚聚氧乙烯醚(OP-10)、十二烷基硫酸钠(SDS) 或十八烷醇基聚氧乙烯醚中的一种或多种；所述二氧化硅与钛酸四丁酯的质量比为1:2。
步骤(5)中所述纳米核壳颗粒、5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因与十六烷基三乙氧基硅烷的质量比为100:8:10。
一种具有抗菌、疏水性的纳米核壳复合颗粒的应用，所述具有抗菌、疏水性的纳米核壳复合颗粒用于制备高效抗菌、无氟、疏水的可降解膜。
一种具有抗菌、疏水性的可降解膜，所述可降解膜的制备方法为：将静电纺丝的纤维膜浸渍含有所述纳米核壳复合颗粒的整理液，之后经过浸轧工艺，制得具有抗菌、疏水性的可降解膜。所述整理液浓度为6～10wt％。
所述纤维膜由聚羟基丁酸酯和聚己内酯按不同比例通过静电纺丝制成。
本发明有益的技术效果在于：
纳米材料由于它的尺寸小和比表面积大等特点，使其具有许多物理和化学特性。目前，纳米材料被研究者广泛关注，运用在生物医学、化学材料、工程学等各个领域。而核壳纳米颗粒有不同材质以核壳结构组成，具有化学和胶体稳定性，催化稳定性强、组件颗粒可控等优点，逐渐成为一个研究热点。此外，据疏水模型，且二氧化硅的可控制备，其常被用来构筑材料表面粗糙度。
本发明通过控制在氨水和乙醇混合溶液中比例，来使四乙氧基硅烷水解制备不同尺寸的纳米二氧化硅作为纳米核壳颗粒的核心。引入二氧化钛作为纳米核壳颗粒的壳层来提高纳米复合颗粒的耐紫外性能。此外，据疏水模型，在纳米核壳颗粒表面接枝疏水剂，来构筑多级粗糙度提高疏水效果。同时引入抗菌剂赋予抗菌性能。使疏水和抗菌效果发挥出协同作用。鉴于此，研究出高效抗菌疏水纳米核壳材料。
本发明用聚羟基丁酸酯和聚己内酯作为原料，通过静电纺丝法制备了可降解的纤维膜基材，并将纳米复合颗粒通过简单的轧烘焙工艺处理到纤维膜上，制备了高效抗菌性能和高疏水性的生物可降解膜，具有十分重要的意义。
附图说明
图1为实施例2所得纳米核壳复合颗粒的透射电镜图和红外图。
图中：(a)是二氧化硅颗粒透射电镜图，(b)是二氧化硅@二氧化钛颗粒透射电镜图，(c)是二氧化硅@二氧化钛复合颗粒透射电镜图，(d)是(a，b，c) 颗粒的红外图。
图2为实施例3所得抗菌疏水纤维膜的疏水效果图。
图中：(a)是未改性纤维膜的疏水效果图，(b)是改性未氯化纤维膜的疏水效果图，(c)是实施例3改性氯化纤维膜的疏水效果图。
图3为实施例3所得抗菌疏水纤维膜的耐紫外稳定性和储存稳定性图。
图中：(a)是实施例3抗菌疏水纤维膜的耐紫外稳定性图，(b)是实施例3 抗菌疏水纤维膜的储存稳定性图。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1
一种具有抗菌、疏水性的可降解膜，其制备方法包括如下步骤：
(1)将5,5-二甲基海因和氢氧化钠溶解于无水乙醇中并在90℃条件下搅拌反应10min，之后除去溶剂乙醇，真空干燥，制得5,5-二甲基海因钠盐；
(2)将步骤(1)制得的5,5-二甲基海因钠盐溶于N,N-二甲基甲酰胺中，加入γ-氯丙基三乙氧基硅烷，95℃冷凝回流反应8h，过滤、除溶剂，得到5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因；
(3)将四乙氧基硅烷加入氨水、水与乙醇的混合溶液中，其中氨水，水与乙醇的混合溶液中质量比为1:1:8，并在60℃条件下反应2h，之后离心分离出二氧化硅；
(4)将步骤(3)制得的二氧化硅分散在乙醇水溶液中，并加入乳化剂OP-10 或SDS，分散均匀后将钛酸四丁酯滴加到混合溶液中，在50℃条件下反应8h，之后离心分离出二氧化硅@二氧化钛纳米核壳颗粒；
(5)将步骤(4)制得的二氧化硅@二氧化钛纳米核壳颗粒在乙醇水溶液中超声分散均匀后，加入步骤(2)制得的5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因和十六烷基三乙氧基硅烷，室温下搅拌8h，之后离心分离出具有抗菌无氟疏水的改性纳米核壳复合颗粒。
(6)将聚羟基丁酸酯和聚己内酯通过静电纺丝制备纤维膜，浸渍在改性纳米核壳复合颗粒配制成的整理液中(乙醇溶剂，浓度6％)，浴比为50：1，再加入1wt％的偶氮二异丁氰，将纤维膜浸渍透后，二浸二轧(轧余率75％)，65℃烘1h，然后水洗烘干；再将烘干的纤维膜浸渍10wt％的次氯酸钠溶液1h，充分水洗后在45℃烘1h，制得具有抗菌、疏水性的可降解膜。
实施例2
一种具有抗菌、疏水性的可降解膜，其制备方法包括如下步骤：
(1)将5,5-二甲基海因和氢氧化钠溶解于无水乙醇中并在90℃条件下搅拌反应10min，之后除去溶剂乙醇，真空干燥，制得5,5-二甲基海因钠盐；
(2)将步骤(1)制得的5,5-二甲基海因钠盐溶于N,N-二甲基甲酰胺中，加入γ-氯丙基三乙氧基硅烷，95℃冷凝回流反应8h，过滤、除溶剂，得到5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因；
(3)将四乙氧基硅烷加入氨水、水与乙醇的混合溶液中，其中氨水，水与乙醇的混合溶液中质量比为1:4:5，并在60℃条件下反应2h，之后离心分离出二氧化硅；
(4)将步骤(3)制得的二氧化硅分散在乙醇水溶液中，并加入乳化剂OP-10 或SDS，分散均匀后将钛酸四丁酯滴加到混合溶液中，在50℃条件下反应8h，之后离心分离出二氧化硅@二氧化钛纳米核壳颗粒；
(5)将步骤(4)制得的二氧化硅@二氧化钛纳米核壳颗粒在乙醇水溶液中超声分散均匀后，加入步骤(2)制得的5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因和十六烷基三乙氧基硅烷，室温下搅拌8h，之后离心分离出具有抗菌无氟疏水的改性纳米核壳复合颗粒。
(6)将聚羟基丁酸酯和聚己内酯通过静电纺丝制备纤维膜，浸渍在改性纳米核壳复合颗粒配制成的整理液中(乙醇溶剂，浓度8％)，浴比为50：1，再加入1wt％的偶氮二异丁氰，将纤维膜浸渍透后，二浸二轧(轧余率75％)，65℃烘1h，然后水洗烘干；再将烘干的纤维膜浸渍10wt％的次氯酸钠溶液1h，充分水洗后在45℃烘1h，制得具有抗菌、疏水性的可降解膜。
实施例3
一种具有抗菌、疏水性的可降解膜，其制备方法包括如下步骤：
(1)将5,5-二甲基海因和氢氧化钠溶解于无水乙醇中并在90℃条件下搅拌反应10min，之后除去溶剂乙醇，真空干燥，制得5,5-二甲基海因钠盐；
(2)将步骤(1)制得的5,5-二甲基海因钠盐溶于N,N-二甲基甲酰胺中，加入γ-氯丙基三乙氧基硅烷，95℃冷凝回流反应8h，过滤、除溶剂，得到5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因；
(3)将四乙氧基硅烷加入氨水、水与乙醇的混合溶液中，其中氨水，水与乙醇的混合溶液中质量比为1:6:3，并在60℃条件下反应2h，之后离心分离出二氧化硅；
(4)将步骤(3)制得的二氧化硅分散在乙醇水溶液中，并加入乳化剂OP-10 或SDS，分散均匀后将钛酸四丁酯滴加到混合溶液中，在50℃条件下反应8h，之后离心分离出二氧化硅@二氧化钛纳米核壳颗粒；
(5)将步骤(4)制得的二氧化硅@二氧化钛纳米核壳颗粒在乙醇水溶液中超声分散均匀后，加入步骤(2)制得的5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因和十六烷基三乙氧基硅烷，室温下搅拌8h，之后离心分离出具有抗菌无氟疏水的改性纳米核壳复合颗粒。
(6)将聚羟基丁酸酯和聚己内酯通过静电纺丝制备纤维膜浸渍在改性纳米核壳复合颗粒配制成的整理液中(乙醇溶剂，浓度10％)，浴比为50：1，再加入1wt％的偶氮二异丁氰，将纤维膜浸渍透后，二浸二轧(轧余率75％)，65℃烘1h，然后水洗烘干；再将烘干的纤维膜浸渍10wt％的次氯酸钠溶液1h，充分水洗后在45℃烘1h，制得具有抗菌、疏水性的可降解膜。
测试例1
通过Nicolet is 10傅立叶红外变换光谱仪对实施例2制备得改性纳米核壳复合颗粒进行表征，并用二氧化硅和二氧化硅@二氧化钛作为对照样品进行测试，并用JEM 2100透射电镜对其进行分析，结果参见图1。
由透射电镜图1a-c看出，成功地制备纳米核壳颗粒，平均直径为248nm，其中核直径约为128nm，壳半径约为60nm。此外接枝后纳米核壳颗粒的表面看不出明显的变化。而红外图1d分析可知，抗菌疏水纳米核壳颗粒的曲线上在 2918、2850、1771和1712cm-1出现了新峰，分别为十六烷基硅烷上的C16烷基链的-CH3和-CH2-及5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因上的C＝O的伸缩振动峰。说明成功制备了抗菌疏水纳米核壳颗粒。
测试例2
根据修正的AATCC100-2004抗菌性能测试标准所述方法进行测试。按照实施例3所制备的具有抗菌、疏水性的可降解膜，并用未改性的纤维膜和最后未经次氯酸钠溶液处理反应的纤维膜作为对照样品进行抗菌测试，接种细菌为金黄色葡萄球菌和大肠杆菌O157：H7，测试结果如表1所示。
表1
注：金黄色葡萄球菌的接种浓度1.03×106CFU/sample；大肠杆菌O157：H7的接种浓度为1.00×106 CFU/sample。
由表1可以发现，实施例3所制备的抗菌疏水纤维膜相比于未改性的纤维膜和未经次氯酸氯化处理的纤维膜，其具有优异的杀菌性能，在接触两种细菌5 min后，能杀死100％的金黄色葡萄球菌和94.77％的大肠杆菌O157：H7。接触 60min能够全部杀死大肠杆菌O157：H7。
测试例3
对实施例3所得具有抗菌、疏水性的可降解膜进行接触角测试，采用DigitalMicroscope Contact Angle Tester测试，其水滴为2μL，并用未改性的纤维膜和最后未经次氯酸钠溶液处理反应的纤维膜作为对照样品进行测试，测试结果如图2 所示。可以发现未改性的纤维膜表面被水珠润湿，而改性的抗菌疏水纤维膜的接触角高达144°，氯化后没太大变化。
测试例4
对实施例3所得具有抗菌、疏水性的可降解膜进行耐紫外稳定性测试，采用紫外线加速老化测试仪测试.参数设置为：辐射为0.89W/cm2，温度为60℃。储存稳定性是在黑暗坏境里存储。测试结果如图3所示。由图3a可以看出，抗菌纤维具有良好的耐紫外稳定性，经过24h辐照还有0.04wt％氯含量，重氯化能恢复到原来的70.3％。此外，图3b可以看出，纤维膜具有优异的储存稳定性， 60d后还有0.30wt％的氯含量，而且重氯化能恢复原来的97.3％。高效抗菌无氟疏水纤维膜具有良好的耐紫外稳定性和优异的储存稳定性，且具有突出的可恢复性，具有很高的实际应用价值。
上述实施例和测试例所涉及各原料均为市售商品，所使用各仪器设备均为本领域常规设备，其中，金黄色葡萄球菌和大肠杆菌O157：H7购自美国模式培养物集存库(ATCC)。
以上所述的仅是本发明的优选实施方式，本发明不限于以上实施例。可以理解，本领域技术人员在不脱离本发明的精神和构思的前提下直接导出或联想到的其他改进和变化，均应认为包含在本发明的保护范围之内。
Claims (10)
1.一种具有抗菌、疏水性的纳米核壳复合颗粒，其特征在于，所述纳米核壳复合颗粒的制备方法包括如下步骤：
（1）将5,5-二甲基海因和氢氧化钠溶解于无水乙醇中并在90℃条件下搅拌反应10min，之后除去溶剂乙醇，真空干燥，制得5,5-二甲基海因钠盐；
（2）将步骤（1）制得的5,5-二甲基海因钠盐溶于N,N-二甲基甲酰胺中，加入γ-氯丙基三乙氧基硅烷，95℃冷凝回流反应8 h，过滤、除溶剂，得到5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因；
（3）将四乙氧基硅烷加入氨水、水与乙醇的混合溶液中，并在60℃条件下反应2 h，之后离心分离出二氧化硅；
（4）将步骤（3）制得的二氧化硅分散在乙醇水溶液中，并加入乳化剂，分散均匀后将钛酸四丁酯滴加到混合溶液中，在50℃条件下反应8 h，之后离心分离出二氧化硅@二氧化钛纳米核壳颗粒；
（5）将步骤（4）制得的二氧化硅@二氧化钛纳米核壳颗粒在乙醇水溶液中超声分散均匀后，加入步骤（2）制得的5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因和十六烷基三乙氧基硅烷，室温下搅拌8 h，之后离心分离出具有抗菌无氟疏水的改性纳米核壳复合颗粒。
2.根据权利要求1所述的纳米核壳复合颗粒，其特征在于，步骤（1）中所述5,5-二甲基海因与氢氧化钠的摩尔比为1:1。
3.根据权利要求1所述的纳米核壳复合颗粒，其特征在于，步骤（2）中所述5,5-二甲基海因钠盐与γ-氯丙基三乙氧基硅烷的摩尔比为1:1。
4.根据权利要求1所述的纳米核壳复合颗粒，其特征在于，步骤（3）中所述氨水、水与乙醇的混合溶液中质量比为1:1:8，1:2:7，1:4:5或1:6:3；所述氨水的质量浓度为28%。
5.根据权利要求1所述的纳米核壳复合颗粒，其特征在于，步骤（4）中所述乳化剂为烷基酚聚氧乙烯醚、十二烷基硫酸钠、十八烷醇基聚氧乙烯醚中的一种或多种；所述二氧化硅与钛酸四丁酯的质量比为1:2。
6.根据权利要求1所述的纳米核壳复合颗粒，其特征在于，步骤（5）中所述纳米核壳颗粒、5,5-二甲基-3-(3'-三乙氧基硅丙基)-海因与十六烷基三乙氧基硅烷的质量比为100:8:10。
7.一种权利要求1所述的纳米核壳复合颗粒的应用，其特征在于，所述具有抗菌、疏水性的纳米核壳复合颗粒用于制备高效抗菌、无氟、疏水的可降解膜。
8.一种具有抗菌、疏水性的可降解膜，其特征在于，所述可降解膜的制备方法为：将静电纺丝的纤维膜浸渍含有权利要求1~6任一项所述纳米核壳复合颗粒的整理液，之后经过浸轧工艺，制得具有抗菌、疏水性的可降解膜。
9.根据权利要求8所述的可降解膜，其特征在于，所述整理液浓度为6~10wt%。
10.根据权利要求8所述的可降解膜，其特征在于，所述纤维膜由聚羟基丁酸酯和聚己内酯按不同比例通过静电纺丝制成。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810927103.0A CN109183398B (zh) | 2018-08-15 | 2018-08-15 | 一种具有抗菌、疏水性的可降解膜及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810927103.0A CN109183398B (zh) | 2018-08-15 | 2018-08-15 | 一种具有抗菌、疏水性的可降解膜及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109183398A CN109183398A (zh) | 2019-01-11 |
| CN109183398B true CN109183398B (zh) | 2020-05-05 |
Family
ID=64935920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810927103.0A Active CN109183398B (zh) | 2018-08-15 | 2018-08-15 | 一种具有抗菌、疏水性的可降解膜及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109183398B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647152A (zh) * | 2020-12-17 | 2021-04-13 | 太和县昌达工贸有限公司 | 一种可生物降解的抗菌聚酯纤维的制备工艺 |
| CN112813693B (zh) * | 2021-01-26 | 2021-11-02 | 江南大学 | 一种抗菌性能可再生的多功能棉织物及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010621A (zh) * | 2010-11-08 | 2011-04-13 | 华东理工大学 | 一种气相粉体合成过程中原位包覆和表面改性的方法 |
| CN102321974A (zh) * | 2011-07-14 | 2012-01-18 | 陕西科技大学 | 一种超疏水防紫外线纺织品的制备方法 |
| CN104088134A (zh) * | 2014-07-18 | 2014-10-08 | 江南大学 | 一种耐紫外线抗菌织物的制备方法 |
| CN108084494A (zh) * | 2017-12-08 | 2018-05-29 | 中国科学院化学研究所 | 表面接枝抗氧剂分子的功能化纳米二氧化钛及其制备方法 |
-
2018
- 2018-08-15 CN CN201810927103.0A patent/CN109183398B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010621A (zh) * | 2010-11-08 | 2011-04-13 | 华东理工大学 | 一种气相粉体合成过程中原位包覆和表面改性的方法 |
| CN102321974A (zh) * | 2011-07-14 | 2012-01-18 | 陕西科技大学 | 一种超疏水防紫外线纺织品的制备方法 |
| CN104088134A (zh) * | 2014-07-18 | 2014-10-08 | 江南大学 | 一种耐紫外线抗菌织物的制备方法 |
| CN108084494A (zh) * | 2017-12-08 | 2018-05-29 | 中国科学院化学研究所 | 表面接枝抗氧剂分子的功能化纳米二氧化钛及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109183398A (zh) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Hydrothermal synthesis of Ag nanoparticles on the nanocellulose and their antibacterial study | |
| Wahid et al. | A facile construction of bacterial cellulose/ZnO nanocomposite films and their photocatalytic and antibacterial properties | |
| Perelshtein et al. | CuO–cotton nanocomposite: Formation, morphology, and antibacterial activity | |
| US8834917B2 (en) | Nanoparticle composition and process thereof | |
| CN109837734B (zh) | 一种可控疏水的抗菌纤维膜及其制备方法 | |
| Huo et al. | Synthesis and characterization of ZnO/palygorskite | |
| CN103947675B (zh) | 磁性氧化石墨烯纳米复合物及其制备方法和应用 | |
| Krishnaveni et al. | Industrial method of cotton fabric finishing with chitosan–ZnO composite for anti-bacterial and thermal stability | |
| CN109183398B (zh) | 一种具有抗菌、疏水性的可降解膜及其制备方法 | |
| CN100588323C (zh) | 一种造纸白水的高效杀菌剂 | |
| CN105295105B (zh) | 一种具有光催化抗菌性的细菌纤维素基复合材料 | |
| Li et al. | Synthesis of an N-halamine monomer and its application in antimicrobial cellulose via an electron beam irradiation process | |
| CN106192074B (zh) | 一种载有纳米银粒子的氧化石墨烯/海藻复合纤维的制备方法 | |
| Thampi et al. | Functionalization of fabrics with PANI/CuO nanoparticles by precipitation route for anti-bacterial applications | |
| Lin et al. | PHB/PCL fibrous membranes modified with SiO 2@ TiO 2-based core@ shell composite nanoparticles for hydrophobic and antibacterial applications | |
| CN112442893A (zh) | 一种特高效纳米铜抗菌剂及其制备方法 | |
| CN106922732B (zh) | 一种以丝瓜络为基质的杀菌材料的制备方法及用途 | |
| CN108034067A (zh) | 一种细菌纤维素膜/纳米铁复合材料及其制备方法与应用 | |
| Morena et al. | Laccase/TEMPO-mediated bacterial cellulose functionalization: production of paper-silver nanoparticles composite with antimicrobial activity | |
| CN109942751A (zh) | 一种塑料抗菌材料的制备方法 | |
| CN104624054B (zh) | 一种控制膜生物污染杀菌剂的制备方法 | |
| Panthi et al. | Interior synthesizing of ZnO nanoflakes inside nylon‐6 electrospun nanofibers | |
| Wan et al. | PDA/PEI-induced in-situ growth of a lotus leaf-like TiO2 nanoparticle film on N-halamine cotton fabric for photocatalytic, self-cleaning and efficient antibacterial performance | |
| CN112695521B (zh) | 一种卤胺改性抗菌介孔材料及合成方法 | |
| Gao et al. | Preparation, characterization and application of ZnO sol containing quaternary ammonium salts |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240119 Address after: 214000 Milan Garden, Xinwu District, Wuxi City, Jiangsu Province 63-1019 Patentee after: Wuxi Maili Information Technology Co.,Ltd. Address before: 101200 room 205-211526, No. 40, Fuqian West Street, Pinggu town, Pinggu District, Beijing (cluster registration) Patentee before: BEIJING YONGBO TECHNOLOGY CO.,LTD. Effective date of registration: 20240119 Address after: 101200 room 205-211526, No. 40, Fuqian West Street, Pinggu town, Pinggu District, Beijing (cluster registration) Patentee after: BEIJING YONGBO TECHNOLOGY CO.,LTD. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University |