CN105671686B - A kind of preparation method of alginate graphene nano cuprous oxide composite antibacterial fibre - Google Patents
A kind of preparation method of alginate graphene nano cuprous oxide composite antibacterial fibre Download PDFInfo
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- CN105671686B CN105671686B CN201610116439.XA CN201610116439A CN105671686B CN 105671686 B CN105671686 B CN 105671686B CN 201610116439 A CN201610116439 A CN 201610116439A CN 105671686 B CN105671686 B CN 105671686B
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- graphene
- cuprous oxide
- nano cuprous
- alginate
- composite antibacterial
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 60
- 239000000835 fiber Substances 0.000 title claims abstract description 32
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000010443 alginic acid Nutrition 0.000 title abstract description 9
- 229920000615 alginic acid Polymers 0.000 title abstract description 9
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title abstract description 8
- 229940072056 alginate Drugs 0.000 title abstract description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000661 sodium alginate Substances 0.000 claims abstract description 24
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 24
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 6
- 239000008103 glucose Substances 0.000 claims abstract description 6
- 238000007711 solidification Methods 0.000 claims abstract description 6
- 230000008023 solidification Effects 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 230000009514 concussion Effects 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000003111 delayed effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims 1
- 229930003268 Vitamin C Natural products 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 235000019154 vitamin C Nutrition 0.000 claims 1
- 239000011718 vitamin C Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005213 imbibition Methods 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- 229960005070 ascorbic acid Drugs 0.000 abstract description 2
- 235000010323 ascorbic acid Nutrition 0.000 abstract description 2
- 239000011668 ascorbic acid Substances 0.000 abstract description 2
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- -1 graphite Alkene Chemical class 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Chemical class 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000035572 chemosensitivity Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of preparation method of alginate graphene nano cuprous oxide composite antibacterial fibre, it is obtained mixed solution A by the way that Graphene is added to copper salt solution；Then, 59 ︰ 15 by volume, above-mentioned mixed solution A is added in sodium alginate aqueous solution, and add glucose or ascorbic acid to make reducing agent, reaction obtains sodium alginate graphene nano cuprous oxide gel, then obtains spinning solution through negative pressure de-bubble, standing, ageing, then film forming, solidification forming, and through washing, hot-drawn tentering, drying, get product.Alginate graphene nano cuprous oxide composite antibacterial fibre obtained by preparation method of the invention, its consistent internal structure is consistent, nano cuprous oxide size tunable, with good water imbibition and permeability；It is suitable for use as producing functional textile and functional non-woven fabric, with wide market prospects.
Description
Technical field
The present invention relates to a kind of preparation method of composite antibacterial fibre, more particularly to a kind of alginate-Graphene-nanometer
The preparation method of cuprous oxide composite antibacterial fibre.
Background technology
Graphene is most thin, a kind of novel nano-material that most hard, electrical and thermal conductivity performance is most strong having now been found that, is praised
It is " dark fund " or " king of new material ".In potential application aspect, Graphene shows wonderful prospect.
First, the Graphene substitute for being to turn into silicon most potential at present, manufactures ultra micro transistor npn npn, for producing not
The supercomputer for coming.Analyzed according to associated specialist, silicon is replaced with Graphene, the speed of service of computer processor will be hundreds of soon
Times.And recently, the scientist of Massachusetts Institute Technology has found that under specific circumstances, Graphene can be converted by studying
Into the topological insulator with unique function.This research finds, is expected to bring a kind of new method for manufacturing quantum computer.
Secondly, Graphene energy power-assisted ultracapacitor, the development of lithium ion battery.Shown according to related data, add graphite
Alkene material, the capacity of extendible more than 5 times of the electric capacity of equal volume, and addition Graphene then can be carried significantly in electrode of lithium cell
Its electric conductivity high.It is reported that the automobile batteries produced using Graphene polymeric material, is expected to reach so surprising effect
Really：Only charge a few minutes, it is possible to allow automobile continuously to start 1000 kilometers.
Additionally, Graphene applies also for circuit, touch-screen, gene sequencing.Graphene intensity exceeds steel decades of times, has
Prestige is used for manufacture ultra light aircraft material, super tough and tensile flak jackets etc..
Graphene has very strong chemosensitivity, can be made high-detectivity detector etc..The sensor for scribbling Graphene can
To detect the steam containing the low concentration for chemical substances such as explosive, ammonia.
It is surprising that Chinese Scientists find that bacterial cell cannot grow on the paper of Graphene, and human cell
Then it is not damaged.Can be utilized to make bandage, packaging for foodstuff even antibiosis T-shirt shirt etc. using this point.
In addition, on the one hand, Graphene is almost fully transparent, 2.3% light is only absorbed.On the other hand, it is caused very much
It is close, even the gas atom (helium atom) of minimum cannot also be penetrated.These features cause that it is highly suitable as opaque products
Raw material, such as transparent touch display screen of electronic product, luminescent screen and solar panel, Textile material, medical membrane material
Material etc..
But, so far, prepared by the Graphene of large area is always a world-famous puzzle, and on December 1st, 2009 is in the U.S.
In the material science international conference held, Japanese fujitsu is announced, unstrpped gas is blowed to scribble in advance and is used as catalyst by they
Iron substrate, be made the graphene film of high-quality 7.5 cm diameter.
But 7.5 centimetres can still be very limited using upper.If prepared as continuous phase using macromolecular material continuous
Film, but the coating function of macromolecular material greatly reduces the anti-microbial property of Graphene again.In addition, the compactness of pure Graphene makes
It is obtained without gas permeability, this is a kind of defect as medical film material.
The content of the invention
It is an object of the present invention to provide one kind with macromolecular sodium alginate as continuous phase, doping deposition nano cuprous oxide
Graphene, prepare good biocompatibility, good permeability, anti-microbial property it is excellent, can with the alginate of arbitrary continuation film forming-
The method of Graphene-nano cuprous oxide composite antibacterial fibre；The method has that technological process is short, technology controlling and process is easy, production
With low cost the features such as.The technical scheme that is used to achieve the above object of the present invention is, a kind of alginate-Graphene-receive
The preparation method of rice cuprous oxide composite antibacterial fibre, it is characterised in that comprise the following steps：
The first step, it is the sodium alginate aqueous solution and mass percent concentration of 2-7% that mass percent concentration is prepared respectively
It is 10% copper salt solution, it is standby；
Second step, microwave concussion or high-speed stirred under, to above-mentioned copper salt solution in, be slowly added to Graphene, and protect
Microwave concussion or high-speed stirred 30-120min are held, mixed solution A is obtained；
Wherein, mass fraction of the Graphene in mixed solution A is 5%-20%；
3rd step, under ultrasonic oscillation or high-speed stirred, the ratio of 5-9 ︰ 1-5, molten by above-mentioned mixing by volume
Liquid A is slowly added into above-mentioned sodium alginate aqueous solution；
Then, at 20 DEG C -100 DEG C, in the ratio that the mol ratio with copper ion is 1 ︰ 1-1.5, glucose or anti-is added
Bad hematic acid makees reducing agent, and reduction reaction 30-60min obtains sodium alginate-Graphene-nano cuprous oxide gel；
By the de-bubble of gained gel negative pressure, stand, then be aged 24-48h, obtain spinning solution；
4th step, by resulting spinning solution through nozzle aperture extrude, and mass percent concentration for 1-5%+divalent
Metal salt bath solution in solidification forming；
Heated stretching, drying, get product again.
The technical effect directly brought by the technical proposal is that,
On the one hand, because continuous phase is macromolecular sodium alginate so that anti-bacterial fibre has good water imbibition and breathes freely
Performance.
On the other hand, due to carrying carboxyl anion on sodium alginate macromolecular chain, nano cuprous oxide can be produced
Positioning action, so that its uniform deposition is on Graphene；
Also, due to being repelled each other between sodium alginate macromolecular chain and macromolecular chain, can effectively suppress/prevent deposition
Nano cuprous oxide on Graphene is grown up.So as to, it is ensured that nano cuprous oxide uniform deposition is coagulating on Graphene
It is dispersed in glue spinning solution, do not assemble, and in follow-up solidification forming, it is consistent to obtain consistent internal structure, nano oxidized
Cuprous size tunable, the good sodium alginate-Graphene-nano cuprous oxide composite antibacterial fibre of permeability.
It is not difficult to find out, the core technology thought of above-mentioned technical proposal is exactly：With sodium alginate gel as carrier, so that graphite
Alkene is uniformly distributed therein, and causes that nano cuprous oxide uniform deposition on Graphene, prepares spinning solution, so be obtained with
Alginate (calcium alginate/alginic acid zinc, and may because reaction carry out caused by degree, remaining, a small amount of sodium alginate into
Point) it is the alginate-Graphene-nano cuprous oxide composite antibacterial fibre product of base material.
Above-mentioned technical proposal preferably solves Graphene and all very big material of both specific surface areas of nano cuprous oxide
Material, between each of which, and each other, (placement) together in the case of, it is impossible to the serious clustering phenomena for avoiding
Occur
And in turn result in and cannot pass through micron-sized spinneret orifice, to complete the technical barrier of wet spinning shaping.
Because Graphene, graphene oxide and nano cuprous oxide specific surface area are all very big, by the one kind in them or
Two or more mixtures put together or occur serious clustering phenomena (is difficult to obtain nano cuprous oxide to be deposited on Graphene
Go up and be evenly distributed on the spinning solution in algal polysaccharides slaine continuous phase), due to being easy to block micron-sized spinneret
Hole, so nano cuprous oxide deposited graphite alkene composite spinning fiber cannot be obtained.
Above-mentioned technical proposal dexterously utilizes the carboxyl anion on macromolecular sodium alginate macromolecular chain, on the one hand to receiving
Rice cuprous oxide deposited graphite alkene has positioning action, is repelled each other away to receiving between another aspect sodium alginate macromolecular chain
The particulate growth of rice cuprous oxide deposited graphite alkene serves interception, so nano cuprous oxide deposited graphite alkene is in gel
It is dispersed in spinning solution, do not assemble, spinneret orifice is not blocked up, can smoothly obtain composite antibacterial fibre.
Why this exactly above-mentioned technical proposal can obtain alginate-Graphene-nano oxidized Asia through wet spinning
The key point of copper composite antibacterial fibre.Also, in above-mentioned technical proposal, used with macromolecular sodium alginate as continuous phase
Alginate-Graphene-nano cuprous oxide composite antibacterial fibre that the method for wet spinning is obtained, is easy to industrialized production.
Additionally, by the excellent nano cuprous oxide uniform deposition of anti-microbial property to Graphene, and then the two is distributed on
In composite fibre with alginate as base material, there is good water imbibition and permeability using macromolecular alginate, compared with
Solve conventional polymer material well to be coated on Graphene, formed " separation layer ", to Graphene and nano cuprous oxide and
The inhibition that anti-microbial property is played.
And, the technological process of above-mentioned technical proposal is simple, technological operation is easy with control, and primary raw material is with low cost,
Manufacturing cost is low.
Preferably, above-mentioned mantoquita refers to copper sulphate, copper nitrate, copper chloride or other water-soluble mantoquitas.
What the optimal technical scheme was directly brought has the technical effect that, raw material sources are wide, low cost, it is easy to obtain.
Further preferably, above-mentioned Graphene is graphene oxide.
What the optimal technical scheme was directly brought has the technical effect that, it is oxidized after Graphene, its oxygen-containing functional group increases,
Property is more active compared with Graphene.So, the whole reaction speed of quickening is not only improved, is conducive to further improving product matter again
Amount.
Further preferably, the slaine of above-mentioned+divalent is CaCl2And/or ZnSO4。
What the optimal technical scheme was directly brought has the technical effect that, CaCl2And/or ZnSO4Good water solubility, ion polarity are strong,
Solidification forming speed is fast, good biocompatibility.
Further preferably, above-mentioned nano cuprous oxide is deposited on Graphene, and the average grain diameter of nano cuprous oxide≤
30nm。
What the optimal technical scheme was directly brought has the technical effect that, the average grain diameter≤30nm of nano cuprous oxide, can be with
Ensure that it has very huge specific surface area, so that it is guaranteed that the inhibition zone radius >=20mm of composite antibacterial fibre product, has
Good anti-microbial property.
Generally, the alginate-Graphene obtained by above-mentioned technical proposal-nano cuprous oxide composite antibacterial is fine
Tie up, its fibrous inner structure form is：With macromolecular sodium alginate as continuous phase, obtained indirectly random length Graphene or
Person's graphene oxide fiber；And on Graphene or graphene oxide fiber, there is uniform deposition to have particle diameter below 30 nanometers, it is anti-
The nano cuprous oxide of bacterium excellent performance.The composite antibacterial fibre of this structure type can be not only used for producing functional textile,
It also is used as producing functional non-woven fabric.
In sum, the present invention has the advantages that relative to prior art：
1st, with macromolecular alginate as continuous phase, the Graphene of doping deposition nano cuprous oxide prepares biofacies
Alginate-Graphene-nano cuprous oxide composite antibacterial fibre that capacitive is good, good permeability, anti-microbial property are excellent.
That is, prior art presence is preferably solved, because of Graphene and nano cuprous oxide both specific surface areas all
Very big material, between each of which, and each other, (placement) together in the case of, it is impossible to what is avoided is serious poly-
Collect the generation of phenomenon, and in turn result in and cannot pass through micron-sized spinneret orifice, to complete the technology of wet spinning shaping
Problem.
Because Graphene, graphene oxide and nano cuprous oxide specific surface area are all very big, by the one kind in them or
Two or more mixtures put together or occur serious clustering phenomena (is difficult to obtain nano cuprous oxide to be deposited on Graphene
Go up and be evenly distributed on the spinning solution in algal polysaccharides slaine continuous phase), due to being easy to block micron-sized spinneret
Hole, so nano cuprous oxide deposited graphite alkene composite spinning fiber cannot be obtained.
The present invention is on the one hand heavy to nano cuprous oxide using the carboxyl anion on macromolecular sodium alginate macromolecular chain
Product Graphene has positioning action, is repelled each other between another aspect sodium alginate macromolecular chain away from heavy to nano cuprous oxide
The particulate growth of product Graphene serves interception, so nano cuprous oxide deposited graphite alkene is uniform in gel spinning liquid
Dispersion, does not assemble, and does not block up spinneret orifice, can smoothly obtain composite antibacterial fibre.
2nd, the gas permeability of product, good water absorption, anti-microbial property are good.
3rd, technological process is short, technology controlling and process is easy, low production cost.
Brief description of the drawings
Fig. 1 is alginate-Graphene obtained in embodiment 1-nano cuprous oxide composite antibacterial fibre inhibition zone picture；
Fig. 2 is the Electronic Speculum of alginate-Graphene obtained in embodiment 1-nano cuprous oxide composite antibacterial fibre section
Photo (multiplication factor is 300,000 times).
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Preparation method is as follows：
The first step, prepares that mass percent concentration is 5% sodium alginate aqueous solution and mass percent concentration is respectively
10% copper-bath, it is standby；
Second step, microwave concussion or high-speed stirred under, to above-mentioned copper salt solution in, be slowly added to Graphene, and protect
Microwave concussion or high-speed stirred 60min are held, mixed solution A is obtained；
Wherein, mass fraction of the Graphene in mixed solution A is 10%；
3rd step, under ultrasonic oscillation or high-speed stirred, the ratio of 7 ︰ 4, above-mentioned mixed solution A is delayed by volume
Slowly it is added in above-mentioned sodium alginate aqueous solution；
Then, at 40 DEG C, in the ratio that the mol ratio with copper ion is 1 ︰ 1.2, ascorbic acid is added to make reducing agent, also
Original reaction 45min, obtains sodium alginate-Graphene-nano cuprous oxide gel；
By the de-bubble of gained gel negative pressure, stand, then be aged 36h, obtain spinning solution；
4th step, resulting spinning solution is extruded through nozzle aperture, and be 1.5% in mass percent concentration
CaCl2Solidification forming in body lotion；
Heated stretching, drying again, obtains final product alginate-Graphene-nano cuprous oxide composite antibacterial fibre.
Embodiment 2
Only 5% sodium alginate aqueous solution is replaced as outside 2% sodium alginate aqueous solution；Remaining, same embodiment
1。
Embodiment 3
Only 5% sodium alginate aqueous solution is replaced as outside 7% sodium alginate aqueous solution；Remaining, same embodiment
1。
Embodiment 4
Only 10% graphene oxide is replaced as outside 5% graphene oxide；Remaining, with embodiment 1.
Embodiment 5
Only 10% graphene oxide is replaced as outside 20% graphene oxide；Remaining, with embodiment 1.
Embodiment 6
With embodiment 1, only 10% graphene oxide is replaced as outside 10% Graphene；Remaining, with embodiment 1.
Embodiment 7
Only the graphene oxide of ultrasonic oscillation 10% is replaced as outside high-speed stirred；Remaining, with embodiment 1.
Embodiment 8
Only by A：B Volume fractions are 7：4 are replaced as 9：Outside 5；Remaining, with embodiment 1.
Embodiment 9
Only by A：B Volume fractions are 7：4 are replaced as 5：Outside 1；Remaining, with embodiment 1.
Embodiment 10
Only by A：B Volume fractions are 7：4 are replaced as 4：Outside 3；Remaining, with embodiment 1.
Embodiment 11
Only by the process for preparation of mixed solution A, the time of microwave concussion or high-speed stirred is replaced as by 60min
Outside 30min；Remaining, with embodiment 1.
Embodiment 12
Only by the process for preparation of mixed solution A, the time of microwave concussion or high-speed stirred is replaced as by 60min
Outside 120min；Remaining, with embodiment 1.
Embodiment 13
Only by copper salt solution by copper-bath, it is replaced as outside copper nitrate solution；Remaining, with embodiment 1.
Embodiment 14
Only by copper-bath, it is replaced as outside copper chloride solution；Remaining, with embodiment 1.
Embodiment 15
" at 20 DEG C, in the ratio that the mol ratio with copper ion is 1 ︰ 1.5, glucose is added to reduce in except the 3rd step
Agent, reduction reaction 45min obtains sodium alginate-Graphene-nano cuprous oxide gel；By gained gel negative pressure de-bubble, quiet
Put, then be aged 24h, obtain spinning solution " outside；Remaining, with embodiment 1.
Embodiment 16
" at 70 DEG C, in the ratio that the mol ratio with copper ion is 1 ︰ 1.3, glucose is added to reduce in except the 3rd step
Agent, reduction reaction 60min obtains sodium alginate-Graphene-nano cuprous oxide gel；By gained gel negative pressure de-bubble, quiet
Put, then be aged 30h, obtain spinning solution " outside；Remaining, with embodiment 1.
Embodiment 17
" at 100 DEG C, in the ratio that the mol ratio with copper ion is 1 ︰ 1.1, glucose is added to reduce in except the 3rd step
Agent, reduction reaction 35min obtains sodium alginate-Graphene-nano cuprous oxide gel；By gained gel negative pressure de-bubble, quiet
Put, then be aged 48h, obtain spinning solution " outside；Remaining, with embodiment 1.
Embodiment 18
, only by 1.5% CaCl2Coagulation bath is replaced as 1% CaCl2Outside coagulation bath；Remaining, same embodiment
1。
Embodiment 19
Only by 1.5% CaCl2Coagulation bath is replaced as 1% CaCl2Outside coagulation bath；Remaining, with embodiment 1.
Embodiment 20
Only by 1.5% CaCl2Coagulation bath is replaced as 5% CaCl2Outside coagulation bath；Remaining, with embodiment 1.
Embodiment 21
Only by 1.5% CaCl2Coagulation bath is replaced as 1% CaCl2ZnSO with 1%4Outside mixing coagulation bath；
Remaining, with embodiment 1.
The detection of product and inspection：
Choosing the product obtained by embodiment 1 carries out staphylococcus aureus antibacterial tests, as a result as shown in figure 1, antibacterial
Circle radius about 25mm.
The fiber product section obtained by embodiment 1 is chosen, under Electronic Speculum, is amplified 300,000 times and is observed, as a result such as Fig. 2
Shown, the particle diameter of nano cuprous oxide is in below 30nm.
Claims (6)
1. a kind of preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre, it is characterised in that including
Following steps：
The first step, prepares mass percent concentration for the sodium alginate aqueous solution and mass percent concentration of 2-7% are respectively
10% copper salt solution, it is standby；
Second step, microwave concussion or high-speed stirred under, to above-mentioned copper salt solution in, be slowly added to Graphene, and keep micro-
Ripple shakes or high-speed stirred 30-120min, obtains mixed solution A；
Wherein, mass fraction of the Graphene in mixed solution A is 5%-20%；
3rd step, under ultrasonic oscillation or high-speed stirred, the ratio of 5-9 ︰ 1-5, above-mentioned mixed solution A is delayed by volume
Slowly it is added in above-mentioned sodium alginate aqueous solution；
Then, at 20 DEG C -100 DEG C, in the ratio that the mol ratio with copper ion is 1 ︰ 1-1.5, glucose or Vitamin C are added
Reducing agent is made in acid, and reduction reaction 30-60min obtains sodium alginate-Graphene-nano cuprous oxide gel；
By the de-bubble of gained gel negative pressure, stand, then be aged 24-48h, obtain spinning solution；
4th step, resulting spinning solution is extruded through nozzle aperture, and mass percent concentration for 1-5%+gold of divalent
Solidification forming in category salt bath solution；
Heated stretching, drying, get product again.
2. the preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre according to claim 1,
Characterized in that, the mantoquita is copper sulphate, copper nitrate, copper chloride or other water-soluble mantoquitas.
3. the preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre according to claim 1,
Characterized in that, the Graphene is graphene oxide.
4. according to the preparation of any described alginate-Graphene-nano cuprous oxide composite antibacterial fibres of claim 1-3
Method, it is characterised in that the slaine of described+divalent is CaCl2And/or ZnSO4。
5. the preparation side of alginate-Graphene-nano cuprous oxide composite antibacterial fibre according to claim 1 and 2
Method, it is characterised in that the nano cuprous oxide is deposited on Graphene, the average grain diameter≤30nm of nano cuprous oxide.
6. the preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre according to claim 3,
Characterized in that, the nano cuprous oxide is deposited on graphene oxide, the average grain diameter≤30nm of nano cuprous oxide.
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| CN108018620A (en) * | 2017-12-13 | 2018-05-11 | 青岛海赛尔新材料科技有限公司 | Antibiotic property sodium zirconium phosphate silver alginate fibre and preparation method thereof |
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