CN105671686A - Preparation method of alginate-graphene-nano-cuprous oxide composite antibacterial fiber - Google Patents
Preparation method of alginate-graphene-nano-cuprous oxide composite antibacterial fiber Download PDFInfo
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- CN105671686A CN105671686A CN201610116439.XA CN201610116439A CN105671686A CN 105671686 A CN105671686 A CN 105671686A CN 201610116439 A CN201610116439 A CN 201610116439A CN 105671686 A CN105671686 A CN 105671686A
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- graphene
- cuprous oxide
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- alginate
- nano cuprous
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 59
- 239000000835 fiber Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 62
- 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 23
- 239000000661 sodium alginate Substances 0.000 claims abstract description 23
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 23
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 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 8
- 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 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 4
- 239000011668 ascorbic acid 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 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 54
- 230000009514 concussion Effects 0.000 claims description 12
- 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 6
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 239000011686 zinc sulphate Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 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
- 239000006210 lotion Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 230000035699 permeability Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 14
- -1 carboxyl anion Chemical class 0.000 description 11
- 230000000845 anti-microbial effect Effects 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 235000010443 alginic acid Nutrition 0.000 description 5
- 229920000615 alginic acid Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 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 description 4
- 229940072056 alginate Drugs 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000001891 gel spinning Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000195474 Sargassum Species 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004531 microgranule 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
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 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
- 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
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 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
- 239000011230 binding agent Substances 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000035572 chemosensitivity Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 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
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 230000001846 repelling effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing 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
Abstract
The invention discloses a preparation method of alginate-graphene-nano-cuprous oxide composite antibacterial fiber. The preparation method comprises the following steps: adding graphene into a copper salt solution to obtain a mixed solution A; then, adding the mixed solution A into a sodium alginate aqueous solution in a volume ratio of (5-9):(1-5), adding glucose or ascorbic acid to serve as a reducing agent, reacting to obtain sodium alginate-graphene-nano-cuprous oxide gel, performing negative-pressure bubble removal, standing and aging to obtain spinning liquid, forming a film, condensing to mold, washing with water, performing thermal-pulling tentering, and drying to obtain a finished product. The alginate-graphene-nano-cuprous oxide composite antibacterial fiber prepared with the preparation method has a uniform and consistent internal structure, is controllable in nano-cuprous oxide particle size, and has very high water-absorbing quality and air permeability; the preparation method is suitable for producing functional textiles and functional non-woven fabrics, and has a wide market prospect.
Description
Technical field
The preparation method that the present invention relates to a kind of composite antibacterial fibre, the preparation method particularly relating to a kind of alginate-Graphene-nano cuprous oxide composite antibacterial fibre.
Background technology
Graphene is the thinnest, the hardest, a kind of novel nano-material that electrical and thermal conductivity performance is the strongest that have now been found that, is described as " dark fund " or " king of new material ". In potential application aspect, Graphene shows wonderful prospect.
First, Graphene is the most potential succedaneum being to become silicon at present, manufactures superminiature transistor, is used for producing the supercomputer in future. According to associated specialist analysis, replacing silicon with Graphene, the speed of service of computer processor will hundreds times soon. And recently, the scientist of Massachusetts Institute Technology finds by studying, under specific circumstances, Graphene can be converted to the topological insulator with unique function. This research finds, is expected to bring a kind of new method manufacturing quantum computer.
Secondly, the development of Graphene energy power-assisted ultracapacitor, lithium ion battery. Show according to related data, add grapheme material, the capacity of extendible more than 5 times of the electric capacity of equal volume, electrode of lithium cell adds Graphene and then can increase substantially its electric conductivity. It is reported that the automobile batteries utilizing Graphene polymeric material to produce is expected to reach so surprising effect: only charge a few minutes, it is possible to allow automobile start 1000 kilometers continuously.
Additionally, Graphene applies also for circuit, touch screen, gene sequencing. Graphene intensity exceeds iron and steel decades of times, is expected to be used to manufacture ultra light aircraft material, super tough and tensile flak jackets etc.
Graphene has very strong chemosensitivity, it is possible to make high-detectivity detector etc. The sensor scribbling Graphene can detect the steam containing the low concentration for the chemical substance such as explosive, ammonia.
It is surprising that Chinese Scientists finds that bacterial cell cannot grow on the paper of Graphene, human cell is then not damaged. Utilize this point can be utilized to make binder, packaging for foodstuff even antibiosis T-shirt shirt etc.
Additionally, on the one hand, Graphene is almost fully transparent, the light of 2.3% is only absorbed. On the other hand, it is very fine and close, even minimum gas atom (helium atom) also cannot penetrate. These features make it be highly suitable as the raw material of opaque products, touch display screen as transparent in electronic product, luminous plaque and solar panel, Textile material, medical film material etc.
But, so far, the preparation of large-area Graphene is always up a world-famous puzzle, December in 2009 1 day is in the material science international conference that the U.S. holds, Japanese fujitsu is announced, unstrpped gas is blowed to the substrate scribbling the ferrum being used as catalyst in advance by them, is made for the graphene film of high-quality 7.5 cm diameters.
But 7.5 centimetres still can be very limited in application. If preparing continuous film using macromolecular material as continuous phase, but the coating function of macromolecular material greatly reducing again the anti-microbial property of Graphene. It addition, the compactness of pure Graphene makes it without breathability, this is a kind of defect as medical film material.
Summary of the invention
It is an object of the invention to, there is provided a kind of with macromole sodium alginate for continuous phase, the Graphene of doping deposition nano cuprous oxide, prepare good biocompatibility, good permeability, anti-microbial property excellent, can the method for alginate-Graphene-nano cuprous oxide composite antibacterial fibre of arbitrary continuation film forming; The method has the features such as technological process is short, technology controlling and process is easy, low production cost. The present invention be employed technical scheme comprise that for achieving the above object, the preparation method of a kind of alginate-Graphene-nano cuprous oxide composite antibacterial fibre, it is characterised in that comprise the following steps:
The first step, preparation mass percent concentration is the sodium alginate aqueous solution of 2-7% and mass percent concentration is the copper salt solution of 10% respectively, standby;
Second step, under microwave concussion or high-speed stirred, in above-mentioned copper salt solution, is slowly added to Graphene, and keeps microwave concussion or high-speed stirred 30-120min, obtain mixed solution A;
Wherein, Graphene mass fraction in mixed solution A is 5%-20%;
3rd step, under ultrasonic wave concussion or high-speed stirred, the ratio of 5-9 1-5 by volume, above-mentioned mixed solution A is slowly added in above-mentioned sodium alginate aqueous solution;
Then, at 20 DEG C-100 DEG C, in the ratio that mol ratio is 1 1-1.5 with copper ion, add glucose or ascorbic acid makes reducing agent, reduction reaction 30-60min, obtain sodium alginate-Graphene-nano cuprous oxide gel;
By gained gel negative pressure de-bubble, standing, then ageing 24-48h, obtain spinning liquid;
4th step, extrudes obtained spinning liquid through nozzle aperture, and mass percent concentration be 1-5%+the slaine body lotion of divalent in solidification forming;
Then through adding hot-stretch, drying, get product.
What technique scheme was directly brought has the technical effect that,
On the one hand, owing to continuous phase is macromole sodium alginate so that anti-bacterial fibre has good water absorption and permeability.
On the other hand, due on sodium alginate macromolecular chain with carboxyl anion, it is possible to nano cuprous oxide produce positioning action so that its uniform deposition is on Graphene;
Further, owing to repelling each other between sodium alginate macromolecular chain and macromolecular chain, it is possible to effectively suppress/stop growing up of the nano cuprous oxide being deposited on Graphene. Thus, ensure that nano cuprous oxide uniform deposition is on Graphene, and dispersed in gel spinning liquid, do not assemble, and in follow-up solidification forming, obtain consistent internal structure consistent, nano cuprous oxide size tunable, sodium alginate-Graphene-nano cuprous oxide composite antibacterial fibre that permeability is good.
It is not difficult to find out, the core technology thought of technique scheme is exactly: with sodium alginate gel for carrier, so that graphene uniform is dispersed in wherein, and make nano cuprous oxide uniform deposition on Graphene, prepare spinning liquid, and then prepare with alginate (calcium alginate/alginic acid zinc, and be likely to because reaction carries out sodium alginate composition caused by degree, remaining, a small amount of) as the alginate-Graphene-nano cuprous oxide composite antibacterial fibre product of base material.
Technique scheme solves Graphene and all very big material of nano cuprous oxide both specific surface areas preferably, between each of which, and each other, (placement) together when, it is impossible to the generation of the serious clustering phenomena avoided
And in turn result in and cannot pass through micron-sized spinneret orifice, to complete the technical barrier that wet spinning shapes.
Because, Graphene, graphene oxide and nano cuprous oxide specific surface area are all very big, one or more kinds of mixture in them are put together or serious clustering phenomena (being difficult to obtain nano cuprous oxide be deposited on Graphene and be evenly distributed on the spinning liquid in Sargassum polysaccharides slaine continuous phase) occurs, the spinneret orifice micron-sized owing to being easy to blocking, so nano cuprous oxide deposited graphite alkene composite spinning fiber cannot be prepared.
Technique scheme utilizes the carboxyl anion on macromole sodium alginate macromolecular chain dexterously, on the one hand nano cuprous oxide deposited graphite alkene there is positioning action, repel each other between sodium alginate macromolecular chain on the other hand away from, the microgranule growth of nano cuprous oxide deposited graphite alkene is served interception, so nano cuprous oxide deposited graphite alkene is dispersed in gel spinning liquid, do not assemble, not stifled spinneret orifice, composite antibacterial fibre can be obtained smoothly.
This just technique scheme why can obtain the key point of alginate-Graphene-nano cuprous oxide composite antibacterial fibre through wet spinning. Further, in technique scheme, the alginate-Graphene-nano cuprous oxide composite antibacterial fibre that obtains of method being continuous phase wet spinning with macromole sodium alginate adopted, it is simple to industrialized production.
In addition, by on nano cuprous oxide uniform deposition excellent for anti-microbial property to Graphene, and then the two is distributed on alginate for the composite fibre of base material, macromole alginate is utilized to have good water absorption and permeability, solve conventional polymer material preferably and be coated on Graphene, formed " sealing coat ", the inhibition to Graphene and nano cuprous oxide and anti-microbial property performance.
And, the technological process of technique scheme is simple, technological operation and control simplicity, and primary raw material is with low cost, and manufacturing cost is low.
Being preferably, above-mentioned mantoquita refers to copper sulfate, copper nitrate, copper chloride or other water solublity mantoquitas.
What this optimal technical scheme was directly brought has the technical effect that, raw material sources are wide, cost is low, it is easy to obtain.
It is preferred that, above-mentioned Graphene is graphene oxide.
What this optimal technical scheme was directly brought has the technical effect that, the Graphene after oxidized, and its oxygen-containing functional group increases, and character relatively Graphene is more active. So, not only improve the whole response speed of quickening, be conducive to again improving product quality further.
It is preferred that, the slaine of above-mentioned+divalent is CaCl2And/or ZnSO4。
What this optimal technical scheme was directly brought has the technical effect that, CaCl2And/or ZnSO4Good water solubility, ion polarity are strong, and solidification forming speed is fast, good biocompatibility.
It is preferred that, above-mentioned nano cuprous oxide is deposited on Graphene, the mean diameter≤30nm of nano cuprous oxide.
What this optimal technical scheme was directly brought has the technical effect that, mean diameter≤the 30nm of nano cuprous oxide, can 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, there is good anti-microbial property.
Generally, alginate-Graphene-nano cuprous oxide composite antibacterial fibre obtained by technique scheme, its fibrous inner structure form is: with macromole sodium alginate for continuous phase, indirectly obtains Graphene or the graphene oxide fiber of random length; And on Graphene or graphene oxide fiber, have uniform deposition to have particle diameter below 30 nanometers, nano cuprous oxide that anti-microbial property is excellent. The composite antibacterial fibre of this version can be not only used for producing functional textile, it is possible to is used as to produce functional non-woven fabric.
In sum, the present invention, relative to prior art, has the advantages that
1, with macromole alginate for continuous phase, the Graphene of doping deposition nano cuprous oxide, prepare the alginate-Graphene-nano cuprous oxide composite antibacterial fibre of good biocompatibility, good permeability, anti-microbial property excellence.
Namely, solve what prior art existed preferably, because of Graphene and all very big material of nano cuprous oxide both specific surface areas, between each of which, and each other, (placement) together when, it is impossible to the generation of the serious clustering phenomena avoided, and in turn result in and cannot pass through micron-sized spinneret orifice, to complete the technical barrier that wet spinning shapes.
Because, Graphene, graphene oxide and nano cuprous oxide specific surface area are all very big, one or more kinds of mixture in them are put together or serious clustering phenomena (being difficult to obtain nano cuprous oxide be deposited on Graphene and be evenly distributed on the spinning liquid in Sargassum polysaccharides slaine continuous phase) occurs, the spinneret orifice micron-sized owing to being easy to blocking, so nano cuprous oxide deposited graphite alkene composite spinning fiber cannot be prepared.
The present invention utilizes the carboxyl anion on macromole sodium alginate macromolecular chain, on the one hand nano cuprous oxide deposited graphite alkene there is positioning action, repel each other between sodium alginate macromolecular chain on the other hand away from, the microgranule growth of nano cuprous oxide deposited graphite alkene is served interception, so nano cuprous oxide deposited graphite alkene is dispersed in gel spinning liquid, do not assemble, not stifled spinneret orifice, composite antibacterial fibre can be obtained smoothly.
2, the breathability of product, good water absorption, anti-microbial property is good.
3, technological process is short, technology controlling and process is easy, low production cost.
Accompanying drawing explanation
Fig. 1 is alginate-Graphene-nano cuprous oxide composite antibacterial fibre inhibition zone picture that embodiment 1 prepares;
Fig. 2 is the electromicroscopic photograph (amplification is 300,000 times) of alginate-Graphene-nano cuprous oxide composite antibacterial fibre section that embodiment 1 prepares.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Preparation method is as follows:
The first step, respectively preparation mass percent concentration be 5% sodium alginate aqueous solution and mass percent concentration be the copper-bath of 10%, standby;
Second step, under microwave concussion or high-speed stirred, in above-mentioned copper salt solution, is slowly added to Graphene, and keeps microwave concussion or high-speed stirred 60min, obtain mixed solution A;
Wherein, Graphene mass fraction in mixed solution A is 10%;
3rd step, under ultrasonic wave concussion or high-speed stirred, the ratio of 74 by volume, above-mentioned mixed solution A is slowly added in above-mentioned sodium alginate aqueous solution;
Then, at 40 DEG C, in the ratio that mol ratio is 1 1.2 with copper ion, add ascorbic acid and make reducing agent, reduction reaction 45min, obtain sodium alginate-Graphene-nano cuprous oxide gel;
By gained gel negative pressure de-bubble, standing, then ageing 36h, obtain spinning liquid;
4th step, extrudes obtained spinning liquid through nozzle aperture, and is the CaCl of 1.5% at mass percent concentration2Solidification forming in body lotion;
Then through adding hot-stretch, drying, obtain alginate-Graphene-nano cuprous oxide composite antibacterial fibre.
Embodiment 2
Only the sodium alginate aqueous solution of 5% is replaced as outside the sodium alginate aqueous solution of 2%; All the other, all with embodiment 1.
Embodiment 3
Only the sodium alginate aqueous solution of 5% is replaced as outside the sodium alginate aqueous solution of 7%; All the other, all with embodiment 1.
Embodiment 4
Outside only 10% graphene oxide being replaced as 5% graphene oxide; All the other, all with embodiment 1.
Embodiment 5
Outside only 10% graphene oxide being replaced as 20% graphene oxide; All the other, all with embodiment 1.
Embodiment 6
With embodiment 1, outside only 10% graphene oxide being replaced as 10% Graphene; All the other, all with embodiment 1.
Embodiment 7
Outside only ultrasonic wave concussion 10% graphene oxide being replaced as high-speed stirred; All the other, all with embodiment 1.
Embodiment 8
It is only outside 7:4 is replaced as 9:5 by A:B Volume fraction; All the other, all with embodiment 1.
Embodiment 9
It is only outside 7:4 is replaced as 5:1 by A:B Volume fraction; All the other, all with embodiment 1.
Embodiment 10
It is only outside 7:4 is replaced as 4:3 by A:B Volume fraction; All the other, all 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 by outside 60min is replaced as 30min; All the other, all 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 by outside 60min is replaced as 120min; All the other, all with embodiment 1.
Embodiment 13
Only by copper salt solution by copper-bath, it is replaced as outside copper nitrate solution; All the other, all with embodiment 1.
Embodiment 14
Only by copper-bath, it is replaced as outside copper chloride solution; All the other, all with embodiment 1.
Embodiment 15
Except the 3rd step " at 20 DEG C, in the ratio that mol ratio is 1 1.5 with copper ion, adds glucose and makes reducing agent, reduction reaction 45min, obtain sodium alginate-Graphene-nano cuprous oxide gel; By gained gel negative pressure de-bubble, standing, then ageing 24h, obtain spinning liquid " outside; All the other, all with embodiment 1.
Embodiment 16
Except the 3rd step " at 70 DEG C, in the ratio that mol ratio is 1 1.3 with copper ion, adds glucose and makes reducing agent, reduction reaction 60min, obtain sodium alginate-Graphene-nano cuprous oxide gel; By gained gel negative pressure de-bubble, standing, then ageing 30h, obtain spinning liquid " outside; All the other, all with embodiment 1.
Embodiment 17
Except the 3rd step " at 100 DEG C, in the ratio that mol ratio is 1 1.1 with copper ion, adds glucose and makes reducing agent, reduction reaction 35min, obtain sodium alginate-Graphene-nano cuprous oxide gel;By gained gel negative pressure de-bubble, standing, then ageing 48h, obtain spinning liquid " outside; All the other, all with embodiment 1.
Embodiment 18
, only by the CaCl of 1.5%2Coagulation bath is replaced as the CaCl of 1%2Outside coagulation bath; All the other, all with embodiment 1.
Embodiment 19
Only by the CaCl of 1.5%2Coagulation bath is replaced as the CaCl of 1%2Outside coagulation bath; All the other, all with embodiment 1.
Embodiment 20
Only by the CaCl of 1.5%2Coagulation bath is replaced as the CaCl of 5%2Outside coagulation bath; All the other, all with embodiment 1.
Embodiment 21
Only by the CaCl of 1.5%2Coagulation bath is replaced as the CaCl of 1%2With 1% ZnSO4Outside mixing coagulation bath; All the other, all with embodiment 1.
The detection of product and inspection:
Choosing the product obtained by embodiment 1 and carry out staphylococcus aureus antibacterial tests, result is as it is shown in figure 1, inhibition zone radius is about 25mm.
Choosing the fiber product section obtained by embodiment 1, under Electronic Speculum, amplify 300,000 times and observe, result is as in figure 2 it is shown, the particle diameter of nano cuprous oxide is all at below 30nm.
Claims (5)
1. the preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre, it is characterised in that comprise the following steps:
The first step, preparation mass percent concentration is the sodium alginate aqueous solution of 2-7% and mass percent concentration is the copper salt solution of 10% respectively, standby;
Second step, under microwave concussion or high-speed stirred, in above-mentioned copper salt solution, is slowly added to Graphene, and keeps microwave concussion or high-speed stirred 30-120min, obtain mixed solution A;
Wherein, Graphene mass fraction in mixed solution A is 5%-20%;
3rd step, under ultrasonic wave concussion or high-speed stirred, the ratio of 5-9 1-5 by volume, above-mentioned mixed solution A is slowly added in above-mentioned sodium alginate aqueous solution;
Then, at 20 DEG C-100 DEG C, in the ratio that mol ratio is 1 1-1.5 with copper ion, add glucose or ascorbic acid makes reducing agent, reduction reaction 30-60min, obtain sodium alginate-Graphene-nano cuprous oxide gel;
By gained gel negative pressure de-bubble, standing, then ageing 24-48h, obtain spinning liquid;
4th step, extrudes obtained spinning liquid through nozzle aperture, and mass percent concentration be 1-5%+the slaine body lotion of divalent in solidification forming;
Then through adding hot-stretch, drying, get product.
2. the preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre according to claim 1, it is characterised in that described mantoquita is copper sulfate, copper nitrate, copper chloride or other water solublity mantoquitas.
3. the preparation method of alginate-Graphene-nano cuprous oxide composite antibacterial fibre according to claim 1, it is characterised in that described Graphene is graphene oxide.
4. the preparation method according to the arbitrary described alginate-Graphene-nano cuprous oxide composite antibacterial fibre of claim 1-3, it is characterised in that the slaine of described+divalent is CaCl2And/or ZnSO4。
5. the preparation method according to the arbitrary described alginate-Graphene-nano cuprous oxide composite antibacterial fibre of claim 1-3, it is characterised in that described nano cuprous oxide is deposited on Graphene, the mean diameter≤30nm of nano cuprous oxide.
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