CN109837734A - A kind of controllable hydrophobic anti-bacterial fibre film and preparation method thereof - Google Patents
A kind of controllable hydrophobic anti-bacterial fibre film and preparation method thereof Download PDFInfo
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- CN109837734A CN109837734A CN201910098862.5A CN201910098862A CN109837734A CN 109837734 A CN109837734 A CN 109837734A CN 201910098862 A CN201910098862 A CN 201910098862A CN 109837734 A CN109837734 A CN 109837734A
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- bacterial fibre
- fibre film
- tunica fibrosa
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- dimethyl
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 239000000835 fiber Substances 0.000 title claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 halogen amine Chemical class 0.000 claims abstract description 37
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 23
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010612 desalination reaction Methods 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical class ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 229960004592 isopropanol Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000004886 process control Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001646719 Escherichia coli O157:H7 Species 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- FZJCXIDLUFPGPP-UHFFFAOYSA-N propan-2-ol;toluene Chemical compound CC(C)O.CC1=CC=CC=C1 FZJCXIDLUFPGPP-UHFFFAOYSA-N 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- 241001333951 Escherichia coli O157 Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006360 Si—O—N Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004283 biguanides Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a kind of controllable hydrophobic anti-bacterial fibre film, the preparation method of the anti-bacterial fibre film includes the following steps: that (1) prepares 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan；(2) quaternary ammonium salt containing allyl and halogen amine is prepared；(3) electrostatic spinning prepares tunica fibrosa；(4) anti-bacterial fibre film is prepared；(5) controllable hydrophobic antimicrobial tunica fibrosa is prepared.The present invention has been prepared with simple method the quaternary ammonium salt containing allyl and halogen amine, and handles and arrive tunica fibrosa, and usable acid alkali process controls hydrophobicity, prepares the antibacterial hydrophobic tunica fibrosa of degradable green.
Description
Technical field
The present invention relates to antibacterials and hydrophobic material technical field, more particularly, to a kind of controllable hydrophobe halogen amine quaternary ammonium salt of pH
The preparation method of anti-bacterial fibre film.
Background technique
According to investigations, China in 2015 consumes 99.22 hundred million packing cases, 169.85 hundred million meters of adhesive tape and 82.68 hundred million modelings
Material bag；Express delivery in 2016 breaks through 31,200,000,000 for the first time；2017, than 2016 same period increased 35%, it means that more
Rubbish constantly manufactured.Although and traditional packaging material type is more, mainly polyethylene, polypropylene, polyphenyl second
Alkene etc., this kind of material mostly chemical stability is stronger, is difficult to degrade in a natural environment, these rubbish need upper century-old ability complete
Degradable.In addition, these packing materials are difficult to handle, often it is stacked and discards together, easily cause white pollution, be also easy into
It for the growth source of the microorganisms such as bacterium, and easily permeates the ground and polluted underground water, jeopardizes ambient enviroment.
In addition, there is various microorganisms for daily life, endanger very wide.On the one hand, microorganism is mild
Under the conditions of easily cause the decomposition and corruption of material, cause the heavy losses of economic aspect, be especially rich in the food of nutrition, be
The good culture medium of microorganism.On the other hand, pathogenic microorganisms should not be underestimated to the harm of organism, especially in medical domain side
Face easily leads to the generation and infection of disease.Currently, bacterium infection has become one sternly in terms of biomaterial is with field
High problem.
With the raising that people's environmental consciousness and medical condition require, biodegradable material is because in food packaging and biology
On medical domain there is huge application potential gradually to get more and more people's extensive concerning.Therefore, exploitation has the life of antibacterial hydrophobic
Biodegradable material is particularly important.On the one hand, common antibacterial agent includes metal and its oxide, quaternary ammonium salt, quaternary alkylphosphonium salt, biguanides
Class, chitosan and its derivative etc., but above-mentioned antibacterial agent is there are variety of problems, such as generate by-product, and some is in nature not
It is degradable, some antibacterial rates are slow, and germicidal efficiency is low etc..Halamine antibacterial agent is a kind of novel green organic antibacterial agent, very greatly
Drawbacks described above is compensated in degree, has many advantages, such as high-efficiency broad spectrum sterilization, the renewable and safe no pollution of antibacterial functions.Another party
Face has self-cleaning function with prominent hydrophobic material.Currently, the material comprising hydrophilic-hydrophobic is widely used in
Drug release application, Textile Engineering etc..However, these most of fabrics are between hydrophobicity and hydrophily without convertible
Wetability.Importantly, controllable hydrophilic/hydrophobic material multifunctional application is more and more concerned.In consideration of it, developing efficiently anti-
The controllable hydrophobe biodegradable material film of bacterium, has a very important significance.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of controllable hydrophobic anti-bacterial fibre films
And preparation method thereof.The present invention provides the antibacterial agents of a kind of efficiently halogen amine and quaternary ammonium salt, and can be used to prepare pH controllably close
Hydrophobic antimicrobial biological degradable membrane.
Technical scheme is as follows:
A kind of controllable hydrophobic anti-bacterial fibre film, the preparation method of the anti-bacterial fibre film include the following steps:
(1) 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan is prepared；
(2) quaternary ammonium salt containing allyl and halogen amine is prepared；
(3) electrostatic spinning prepares tunica fibrosa；
(4) anti-bacterial fibre film is prepared；
(5) controllable hydrophobic antimicrobial tunica fibrosa is prepared.
3- (2 '-the chloroethyl) -5,5- Dimethyl Hydan the preparation method comprises the following steps:
1. 5- Dimethyl Hydan and sodium hydroxide are dissolved in dehydrated alcohol by 5, it is stirred to react under the conditions of 90 DEG C
80 DEG C are cooled to after 10min；
2. the bromo- 2- chloroethanes of 1-, back flow reaction 8h are added after；
3. the reaction mixture of step 2. is filtered desalination, after revolving removes solvent, liquid separation is carried out using ethyl acetate/water；
4. taking supernatant, revolving removes ethyl acetate, crystalline object is obtained after drying, then recrystallized by iso-propanol/toluene, does
White crystal, as 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan are obtained after dry.
The molar ratio of the 5,5- Dimethyl Hydan, sodium hydroxide and the bromo- 2- chloroethanes of 1- is 1:1:1；The acetic acid second
Ester/water volume ratio is 4/1；The volume ratio of the iso-propanol/toluene is 9/1.
The quaternary ammonium salt containing allyl and halogen amine the preparation method comprises the following steps:
3- (2 '-chloroethyl) -5,5- Dimethyl Hydan is dissolved in n,N-Dimethylformamide, potassium iodide and methyl-prop is added
Olefin(e) acid dimethylaminoethyl, and 1wt% polymerization inhibitor is added, lead to nitrogen reaction for 24 hours, cooled and filtered desalination, revolving removes solvent,
It is purified again by ethyl acetate, is dried to obtain thick substances, the quaternary ammonium salt containing allyl and halogen amine, i.e. 2- (4,4- bis- is made
Methyl -2,5- dioxo alkyl imidazole -1- base)-N- (2- (methacryloxy) ethyl)-N, N- dimethyl -1- ammonium salt.
Mole of 3- (2 '-the chloroethyl) -5,5- Dimethyl Hydan, potassium iodide and dimethylaminoethyl methacrylate
Than for 1:1:1；The polymerization inhibitor is hydroquinone.
The process of the electrostatic spinning are as follows: pass through biodegradable material poly butyric ester and polycaprolactone respectively quiet
Tunica fibrosa is made in Electrospun, later by tunica fibrosa in low temperature plasma instrument, its surface is made to obtain hydrophilic radical hydroxyl and carboxylic
Base.
The technological parameter of the low temperature plasma instrument: under Oxygen Condition, discharge power 100W, pressure 80KPa, when processing
Between 300s.
In step (4) anti-bacterial fibre film the preparation method comprises the following steps:
1. it is water-soluble that the quaternary ammonium salt containing allyl and halogen amine prepared by step (2) is dispersed in the ethyl alcohol containing a small amount of tetrahydrofuran
In liquid, and dimethylaminoethyl methacrylate is added and eight vinyl-POSS are configured to finishing fluid, adds the idol of 1wt%
Two isobutyl cyanogen of nitrogen；
2. tunica fibrosa prepared by step (3) is immersed in step 1. in finishing fluid obtained, pass through second dipping and rolling later, 65
1h is dried under the conditions of DEG C, then washing drying；
3. the tunica fibrosa 2. handled by step is impregnated in 10% aqueous sodium hypochlorite solution, after 1h, 45 DEG C of conditions
Lower drying 1h, obtains anti-bacterial fibre film.
In the mixed solution, ethyl alcohol: water: tetrahydrofuran volume ratio is 4:5:1；The quaternary ammonium salt, methacrylic acid two
The mass ratio of methylamino ethyl ester and eight vinyl-POSS are respectively 3:10:1.3,5:10:1.5 or 8:10:1.8；Two leaching two
The pick-up rolled is 75%.
In step (5) controllable hydrophobic antimicrobial tunica fibrosa the preparation method comprises the following steps: by step (4) preparation antibacterial degradable film soak
For stain after aqueous hydrochloric acid solution or ammonia spirit processing 1h, 45 DEG C of drying 1h obtain hydrophobic/hydrophilic anti-bacterial fibre film；The salt
The mass fraction of aqueous acid is 10%, the 28% of ammonia spirit mass fraction.
The quaternary ammonium salt containing allyl and halogen amine is the compound of structure shown in formula (I):
The present invention is beneficial to be had the technical effect that
The present invention is prepared into a kind of quaternary ammonium salt containing allyl and halogen amine, and the high-efficiency broad spectrum that can not only play halogen amine kills
Bacterium, can also play quaternary ammonium salt stablizes sterilization.By introduce can pH response dimethylaminoethyl methacrylate, a side
Face obtains hydrophilic antimicrobial tunica fibrosa through peracid treatment, shows good hydrophily, and its anti-microbial property is obtained compared to untreated
It is apparent to improve；On the other hand, hydrophobic fiber film is obtained after further alkali process, shows poor antibacterial effect, but its
Excellent hydrophobicity is shown, the self-cleaning ability having had.In addition, eight vinyl-POSS contain 4 as crosslinking agent surface
Vinyl and ethyl have preferable crosslinked action, and can also be improved hydrophobic performance.
The present invention uses poly butyric ester and polycaprolactone as raw material, and degradable fibre is prepared for by method of electrostatic spinning
Film base material is tieed up, and by antibacterial agent, pH responds hydrophobing agent by being prepared for height in eight vinyl-POSS crosslinking Treatments to tunica fibrosa
Imitate anti-bacterial fibre film.It is handled by simple pH solution, so that it may show different hydrophilic and hydrophobics, there is highly important meaning
Justice.
Detailed description of the invention
Fig. 1 is that embodiment 2 prepares the infrared figure of controllable hydrophobe anti-bacterial fibre film and XPS figure；
In figure: A is the FT-IR figure of embodiment 2, and (B) is the XPS figure of embodiment 2；A is untreated tunica fibrosa conduct pair
In the same old way, b is without overchlorinated tunica fibrosa in embodiment 2, and c is the tunica fibrosa after 2 chlorination of embodiment.
Fig. 2 is the hydrophobic effect figure of the tunica fibrosa of embodiment 4 and 5；
In figure: A is water contact angle of the embodiment 4 in different times of contact, and (B) is embodiment 5 in different times of contact
Water contact angle.
Fig. 3 is the resistance to ultraviolet stability and storage stability figure of 3 gained antibacterial hydrophobic tunica fibrosa of embodiment；
In figure: A is the figure of resistance to ultraviolet stability of the controllable hydrophobe anti-bacterial fibre film of embodiment 2, and B is the controllable parent of embodiment 2
The storage stability figure of hydrophobic antimicrobial tunica fibrosa.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
A kind of preparation method of anti-bacterial fibre film includes the following steps:
(1) the 5,5- Dimethyl Hydan of 12.8g (0.1mol) and 4.0g sodium hydroxide are dissolved in 100mL dehydrated alcohol
And 80 DEG C are cooled to after under the conditions of 90 DEG C being stirred to react 10min, by the bromo- 2- chloroethanes of equimolar 1- is added, flow back 8h.By institute
It obtains solution and filters desalination, after revolving removes solvent, after taking supernatant 3 times by ethyl acetate/water (4/1, v/v) liquid separation, revolving is removed
Ethyl acetate is removed, crystalline object is obtained after drying, then recrystallized by isopropanol toluene/(9/1, v/v), white crystalline substance is obtained after dry
Body, as 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan；
(2) 3- made from step (1) (2 '-chloroethyl) -5,5- Dimethyl Hydan is dissolved in the N of 100mL, N- dimethyl methyl
Equimolar potassium iodide and dimethylaminoethyl methacrylate is added in amide, and be added 1wt% polymerization inhibitor (hydroquinone) in
Three-necked flask leads to nitrogen reaction for 24 hours.Cooled and filtered desalination, revolving removes solvent, then is purified by ethyl acetate, is dried to obtain
Thick substances, 2- (4,4- dimethyl -2,5- dioxo alkyl imidazole -1- base)-N- (2- (methacryloxy) ethyl)-N, N-
Dimethyl -1- ammonium salt；
(3) biodegradable material poly butyric ester and polycaprolactone are prepared by 2:3 (w:w) by electrostatic spinning fine
Tie up film.By tunica fibrosa in low temperature plasma instrument, plasma-treating technology parameter: oxygen, discharge power 100W, pressure
80KPa handles time 300s.
(4) quaternary ammonium salt containing allyl and halogen amine made from step (2) is dispersed in ethanol water, and methyl is added
Dimethylaminoethyl acrylate and eight vinyl-POSS be configured to certain density finishing fluid (ethyl alcohol: water: tetrahydrofuran, v:v:
V, 4:5:1), wherein the mass ratio of quaternary ammonium salt, dimethylaminoethyl methacrylate and eight vinyl-POSS is 3:10:1.3,
And the azo-bis-isobutyl cyanide of 1wt% is added, and after tunica fibrosa dip finishing liquid made from step (3), second dipping and rolling (pick-up
75%), 65 DEG C of baking 1h, then washing drying.
(5) after tunica fibrosa made from step (2) being impregnated in 10% aqueous sodium hypochlorite solution 1h, 45℃1h is dried, is obtained
Anti-bacterial fibre film.
Embodiment 2
A kind of preparation method of anti-bacterial fibre film includes the following steps:
(1) the 5,5- Dimethyl Hydan of 12.8g (0.1mol) and 4.0g sodium hydroxide are dissolved in 100mL dehydrated alcohol
And 80 DEG C are cooled to after under the conditions of 90 DEG C being stirred to react 10min, by the bromo- 2- chloroethanes of equimolar 1- is added, flow back 8h.By institute
It obtains solution and filters desalination, after revolving removes solvent, after taking supernatant 3 times by ethyl acetate/water (4/1, v/v) liquid separation, revolving is removed
Ethyl acetate is removed, crystalline object is obtained after drying, then recrystallized by isopropanol toluene/(9/1, v/v), white crystalline substance is obtained after dry
Body, as 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan；
(2) 3- made from step (1) (2 '-chloroethyl) -5,5- Dimethyl Hydan is dissolved in the N of 100mL, N- dimethyl methyl
Equimolar potassium iodide and dimethylaminoethyl methacrylate is added in amide, and be added 1wt% polymerization inhibitor (hydroquinone) in
Three-necked flask leads to nitrogen reaction for 24 hours.Cooled and filtered desalination, revolving removes solvent, then is purified by ethyl acetate, is dried to obtain
Thick substances, 2- (4,4- dimethyl -2,5- dioxo alkyl imidazole -1- base)-N- (2- (methacryloxy) ethyl)-N, N-
Dimethyl -1- ammonium salt；
(3) biodegradable material poly butyric ester and polycaprolactone are passed through into electrostatic spinning system in 2:3 (w:w) ratio
Standby tunica fibrosa.By tunica fibrosa in low temperature plasma instrument, plasma-treating technology parameter: oxygen, discharge power 100W, pressure
Strong 80KPa handles time 300s.
(4) quaternary ammonium salt containing allyl and halogen amine made from step (2) is dispersed in ethanol water, and methyl is added
Dimethylaminoethyl acrylate and eight vinyl-POSS be configured to certain density finishing fluid (ethyl alcohol: water: tetrahydrofuran, v:v:
V, 4:5:1), wherein the mass ratio of quaternary ammonium salt, dimethylaminoethyl methacrylate and eight vinyl-POSS is 5:10:1.5,
And the azo-bis-isobutyl cyanide of 1wt% is added, and after tunica fibrosa dip finishing liquid made from step (3), second dipping and rolling (pick-up
75%), 65 DEG C of baking 1h, then washing drying.
(5) after tunica fibrosa made from step (2) being impregnated in 10% aqueous sodium hypochlorite solution 1h, 45℃1h is dried, is obtained
Anti-bacterial fibre film.
Embodiment 3
A kind of preparation method of anti-bacterial fibre film includes the following steps:
(1) the 5,5- Dimethyl Hydan of 12.8g (0.1mol) and 4.0g sodium hydroxide are dissolved in 100mL dehydrated alcohol
And 80 DEG C are cooled to after under the conditions of 90 DEG C being stirred to react 10min, by the bromo- 2- chloroethanes of equimolar 1- is added, flow back 8h.By institute
It obtains solution and filters desalination, after revolving removes solvent, after taking supernatant 3 times by ethyl acetate/water (4/1, v/v) liquid separation, revolving is removed
Ethyl acetate is removed, crystalline object is obtained after drying, then recrystallized by isopropanol toluene/(9/1, v/v), white crystalline substance is obtained after dry
Body, as 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan；
(2) 3- made from step (1) (2 '-chloroethyl) -5,5- Dimethyl Hydan is dissolved in the N of 100mL, N- dimethyl methyl
Equimolar potassium iodide and dimethylaminoethyl methacrylate is added in amide, and be added 1wt% polymerization inhibitor (hydroquinone) in
Three-necked flask leads to nitrogen reaction for 24 hours.Cooled and filtered desalination, revolving removes solvent, then is purified by ethyl acetate, is dried to obtain
Thick substances, 2- (4,4- dimethyl -2,5- dioxo alkyl imidazole -1- base)-N- (2- (methacryloxy) ethyl)-N, N-
Dimethyl -1- ammonium salt；
(3) biodegradable material poly butyric ester and polycaprolactone are passed through into electrostatic spinning system in 2:3 (w:w) ratio
Standby tunica fibrosa.By tunica fibrosa in low temperature plasma instrument, plasma-treating technology parameter: oxygen, discharge power 100W, pressure
Strong 80KPa handles time 300s.
(4) quaternary ammonium salt containing allyl and halogen amine made from step (2) is dispersed in ethanol water, and methyl is added
Dimethylaminoethyl acrylate and eight vinyl-POSS be configured to certain density finishing fluid (ethyl alcohol: water: tetrahydrofuran, v:v:
V, 4:5:1), wherein the mass ratio of quaternary ammonium salt, dimethylaminoethyl methacrylate and eight vinyl-POSS is 8:10:1.8,
And the azo-bis-isobutyl cyanide of 1wt% is added, and after tunica fibrosa dip finishing liquid made from step (3), second dipping and rolling (pick-up
75%), 65 DEG C of baking 1h, then washing drying.
(5) after tunica fibrosa made from step (2) being impregnated in 10% aqueous sodium hypochlorite solution 1h, 45℃1h is dried, is obtained
Anti-bacterial fibre film.
Embodiment 4
A kind of preparation method of hydrophilic antimicrobial tunica fibrosa includes the following steps:
(1) by antibacterial degradable film immersion as described in example 2 after 10% aqueous hydrochloric acid solution handles 1h, 45 DEG C of drying
1h obtains hydrophilic antimicrobial tunica fibrosa.
Embodiment 5
A kind of preparation method of hydrophobic antimicrobial tunica fibrosa includes the following steps:
(1) by antibacterial degradable film immersion as described in example 2 after the ammonia spirit that mass fraction is 28% handles 1h,
45 DEG C of drying 1h, obtain hydrophobic antimicrobial tunica fibrosa.
Test case 1
Pass through 10 Fourier transform infrared spectrometer of Nicolet is and ESCALAB 250Xi x-ray photoelectron spectroscopy
Instrument prepares the controllable hydrophobe tunica fibrosa of antibacterial to embodiment 2 and characterizes, and with for modified tunica fibrosa and being modified as chlorination processing
Tunica fibrosa is tested as control sample, as a result referring to Fig. 1.
By Figure 1A infrared analysis it is found that the controllable hydrophobe tunica fibrosa of antibacterial is in 801 and 621cm-1There is new peak, respectively
The stretching vibration peak of Si-O-Si and-N-H key on monomer.Figure 1B can be seen that on the XPS spectrum figure of modified fibre film 402,
There is the new peak of N 1s and Si 1s and 2p in 150 and 103eV, and the tunica fibrosa spectrogram of further chlorination Cl occurs in 199eV
The new peak of 2p illustrates successfully to be prepared for the controllable hydrophobe tunica fibrosa of antibacterial.
Test case 2
It is tested according to modified AATCC100-2004 anti-microbial property test standard the method.According to embodiment 2,
Tunica fibrosa prepared by example 4 and example 5, and made with the tunica fibrosa without liquor natrii hypochloritis's processing in unmodified fibers film and example 2
Antibacterial test is carried out for control sample, inoculated bacteria is staphylococcus aureus and Escherichia coli O 157: H7, test result such as table
Shown in 1.
Table 1
Note: the inoculum density 1.13 × 10 of staphylococcus aureus6CFU/sample；Escherichia coli O 157: the inoculation of H7
Concentration is 2.67 × 106CFU/sample。
By table 1 it can be found that modified and chlorination tunica fibrosa is compared to not modified tunica fibrosa and modified non-chlorination processing
Tunica fibrosa, 100% can be killed after contacting staphylococcus aureus 30min with excellent bactericidal property；?
Contact Escherichia coli O 157: after H7 60min, 72.40% can be killed.Modified fibre film through peracid treatment is shown more
Add excellent anti-microbial property, 84.69% Escherichia coli O 157: H7 can be killed.And the modified fibre film Jing Guo alkali process is aobvious
Weaker anti-microbial property is shown.
Test case 3
Digital Microscope Contact Angle is passed through to tunica fibrosa prepared by embodiment 4 and example 5
Tester tests its contact angle, the contact angle after testing its 0,5 and 10min respectively, water droplet 2uL.Test result such as Fig. 2 institute
Show.It can be found that the tunica fibrosa of AMMONIA TREATMENT shows excellent hydrophobic performance, contact angle is 134 °, and has and hold well
Long property.And the tunica fibrosa of HCl treatment shows hydrophily, it can by droplet complete wetting.
Test case 4
Resistance to ultraviolet stability test and stable storing test are carried out to anti-bacterial fibre film prepared by embodiment 2.It is resistance to ultraviolet
Stability test is tested, parameter setting are as follows: radiate as 0.89W/cm using ultraviolet light accelerated ageing tester2, temperature 60
℃；Storage stability is stored in dark bad border.By the ultraviolet radioactive of 12h it can be seen from Fig. 3 A, the chlorine of tunica fibrosa contains
Amount is 0.18wt%, is original 64.3%；After radiating for 24 hours, chlorinity still has 0.12wt%, is original
42.9%, and the chlorinity after chlorination is restored to 0.25wt% (being restored to 89.3%) again.In addition, Fig. 3 B can be seen that fiber
Film has excellent storage stability, and there are also the chlorinities of 0.17wt% after 60d, and chlorination can restore original again
0.26wt% is original 92.9%.Therefore, the controllable hydrophobic antimicrobial fiber of preparation has good resistance to ultraviolet stability and excellent
Different storage stability, and restorability can be splendid.Value with practical application.
Each raw material involved by above-described embodiment and Application Example is commercial goods, and institute is this using each instrument and equipment
Field conventional equipment, wherein staphylococcus aureus and Escherichia coli O 157: H7 is purchased from American Type Culture collection warehousing
(ATCC)。
What has been described above is only a preferred embodiment of the present invention, and present invention is not limited to the above embodiments.It is appreciated that this
The other improvements and change that field technical staff directly exports or associates without departing from the spirit and concept in the present invention
Change, is considered as being included within protection scope of the present invention.
Claims (10)
1. a kind of controllable hydrophobic anti-bacterial fibre film, which is characterized in that the preparation method of the anti-bacterial fibre film includes following step
It is rapid:
(1) 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan is prepared；
(2) quaternary ammonium salt containing allyl and halogen amine is prepared；
(3) electrostatic spinning prepares tunica fibrosa；
(4) anti-bacterial fibre film is prepared；
(5) controllable hydrophobic antimicrobial tunica fibrosa is prepared.
2. anti-bacterial fibre film according to claim 1, which is characterized in that the 3- (2 '-chloroethyl) -5,5- dimethyl sea
Cause the preparation method comprises the following steps:
1. 5- Dimethyl Hydan and sodium hydroxide are dissolved in dehydrated alcohol by 5, after being stirred to react 10min under the conditions of 90 DEG C
It is cooled to 80 DEG C；
2. the bromo- 2- chloroethanes of 1-, back flow reaction 8h are added after；
3. the reaction mixture of step 2. is filtered desalination, after revolving removes solvent, liquid separation is carried out using ethyl acetate/water；
4. taking supernatant, revolving removes ethyl acetate, crystalline object is obtained after drying, then recrystallized by iso-propanol/toluene, after dry
Obtain white crystal, as 3- (2 '-chloroethyl) -5,5- Dimethyl Hydan.
3. anti-bacterial fibre film according to claim 2, which is characterized in that 5, the 5- Dimethyl Hydan, sodium hydroxide with
The molar ratio of the bromo- 2- chloroethanes of 1- is 1:1:1；The volume ratio of the ethyl acetate/water is 4/1；The body of the iso-propanol/toluene
Product is than being 9/1.
4. anti-bacterial fibre film according to claim 1, which is characterized in that the system of the quaternary ammonium salt containing allyl and halogen amine
Preparation Method are as follows:
3- (2 '-chloroethyl) -5,5- Dimethyl Hydan is dissolved in n,N-Dimethylformamide, potassium iodide and methacrylic acid is added
Dimethylaminoethyl, and 1wt% polymerization inhibitor is added, lead to nitrogen reaction for 24 hours, cooled and filtered desalination, revolving removing solvent, then by
Ethyl acetate purification, is dried to obtain thick substances, and the quaternary ammonium salt containing allyl and halogen amine, i.e. 2- (4,4- dimethyl-is made
2,5- dioxo alkyl imidazole -1- base)-N- (2- (methacryloxy) ethyl)-N, N- dimethyl -1- ammonium salt.
5. anti-bacterial fibre film according to claim 4, which is characterized in that the 3- (2 '-chloroethyl) -5,5- dimethyl sea
The molar ratio of cause, potassium iodide and dimethylaminoethyl methacrylate is 1:1:1；The polymerization inhibitor is hydroquinone.
6. anti-bacterial fibre film according to claim 1, which is characterized in that the process of the electrostatic spinning are as follows: can by biology
Tunica fibrosa is made by electrostatic spinning respectively in degradable material poly butyric ester and polycaprolactone (2:3, w:w), later by fiber
Film makes its surface obtain hydrophilic radical hydroxyl and carboxyl in low temperature plasma instrument.
7. anti-bacterial fibre film according to claim 6, which is characterized in that the technological parameter of the low temperature plasma instrument:
Under Oxygen Condition, discharge power 100W, pressure 80KPa handle time 300s.
8. anti-bacterial fibre film according to claim 1, which is characterized in that the preparation method of anti-bacterial fibre film in step (4)
Are as follows:
1. the quaternary ammonium salt containing allyl and halogen amine prepared by step (2) is dispersed in the ethanol water containing a small amount of tetrahydrofuran
In, and dimethylaminoethyl methacrylate is added and eight vinyl-POSS are configured to finishing fluid, add the azo of 1wt%
Two isobutyl cyanogen；
2. tunica fibrosa prepared by step (3) is immersed in step 1. in finishing fluid obtained, pass through second dipping and rolling, 65 DEG C of items later
1h is dried under part, then washing drying；
3. the tunica fibrosa 2. handled by step is impregnated in 10% aqueous sodium hypochlorite solution, after 1h, dried under the conditions of 45 DEG C
Dry 1h, obtains anti-bacterial fibre film.
9. anti-bacterial fibre film according to claim 8, which is characterized in that in the mixed solution, ethyl alcohol: water: tetrahydro furan
Volume ratio of muttering is 4:5:1；The mass ratio of the quaternary ammonium salt, dimethylaminoethyl methacrylate and eight vinyl-POSS is distinguished
For 3:10:1.3,5:10:1.5 or 8:10:1.8；The pick-up of the second dipping and rolling is 75%.
10. controllable hydrophobic antimicrobial tunica fibrosa according to claim 1, which is characterized in that controllable hydrophobic antimicrobial in step (5)
Tunica fibrosa the preparation method comprises the following steps: by step (4) preparation antibacterial degradable film immersion at aqueous hydrochloric acid solution or ammonia spirit
After managing 1h, 45 DEG C of drying 1h obtain hydrophobic/hydrophilic anti-bacterial fibre film；The mass fraction of the aqueous hydrochloric acid solution is 10%, ammonium hydroxide
The 28% of liquid quality fraction.
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| CN110331579A (en) * | 2019-06-21 | 2019-10-15 | 广东工业大学 | A kind of surface-functionalized Oligoanilines nanofiber of antibacterial and its preparation method and application |
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| CN114438665A (en) * | 2022-01-28 | 2022-05-06 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial non-woven fabric and preparation method thereof |
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| CN116377719A (en) * | 2023-04-11 | 2023-07-04 | 安徽新虹新材料科技有限公司 | High-modulus water-washing-resistant antibacterial cotton yarn |
| CN116574202A (en) * | 2023-04-12 | 2023-08-11 | 华南理工大学 | Hydantoin structure-containing chitosan biquaternary ammonium salt antibacterial agent and preparation method and application thereof |
| CN116574202B (en) * | 2023-04-12 | 2024-05-10 | 华南理工大学 | Hydantoin structure-containing chitosan biquaternary ammonium salt antibacterial agent and preparation method and application thereof |
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