CN115710759B - Absorbable hollow fiber - Google Patents
Absorbable hollow fiber Download PDFInfo
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- CN115710759B CN115710759B CN202211448430.0A CN202211448430A CN115710759B CN 115710759 B CN115710759 B CN 115710759B CN 202211448430 A CN202211448430 A CN 202211448430A CN 115710759 B CN115710759 B CN 115710759B
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- sodium alginate
- hollow fiber
- nano silver
- modified starch
- starch
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 69
- 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 129
- 239000000661 sodium alginate Substances 0.000 claims abstract description 128
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 128
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 128
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920000881 Modified starch Polymers 0.000 claims abstract description 63
- 239000004368 Modified starch Substances 0.000 claims abstract description 63
- 235000019426 modified starch Nutrition 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003094 microcapsule Substances 0.000 claims abstract description 58
- 108010010803 Gelatin Proteins 0.000 claims abstract description 37
- 229920000159 gelatin Polymers 0.000 claims abstract description 37
- 239000008273 gelatin Substances 0.000 claims abstract description 37
- 235000019322 gelatine Nutrition 0.000 claims abstract description 37
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 50
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 46
- 229920002472 Starch Polymers 0.000 claims description 37
- 235000019698 starch Nutrition 0.000 claims description 37
- 239000008107 starch Substances 0.000 claims description 37
- 229920001661 Chitosan Polymers 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims description 27
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 27
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 27
- 239000011162 core material Substances 0.000 claims description 26
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- 239000001110 calcium chloride Substances 0.000 claims description 24
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 24
- 241001122767 Theaceae Species 0.000 claims description 23
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 23
- 235000013824 polyphenols Nutrition 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 206010016807 Fluid retention Diseases 0.000 abstract description 52
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 36
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 42
- 229940032147 starch Drugs 0.000 description 29
- 239000000243 solution Substances 0.000 description 21
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 230000001954 sterilising effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004659 sterilization and disinfection Methods 0.000 description 11
- 229920001592 potato starch Polymers 0.000 description 10
- 229910001923 silver oxide Inorganic materials 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 235000011148 calcium chloride Nutrition 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229940080313 sodium starch Drugs 0.000 description 5
- 229960002713 calcium chloride Drugs 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000035587 bioadhesion Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- -1 glycerin fatty acid ester Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013882 gravy Nutrition 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to the technical field of functional composite materials, and particularly discloses an absorbable hollow fiber. The absorbable hollow fiber comprises, by weight, 6-12 parts of sodium alginate modified starch, 3-9 parts of gelatin and 2-8 parts of nano silver microcapsule; the sodium alginate modified starch has stronger water absorbability and adhesiveness, and the sodium alginate modified starch is dispersed in the gaps of the gelatin mesh structure to form a compact crosslinked structure, so that the adhesiveness, water absorbability and water retention of the hollow fiber are further improved; the nano silver microcapsule has a bactericidal effect, and the sodium alginate modified starch further promotes the cohesiveness of the nano silver microcapsule and gelatin molecules, so that the bactericidal performance of the prepared hollow fiber is durable.
Description
Technical Field
The application belongs to the technical field of functional composite materials, and particularly relates to an absorbable hollow fiber.
Background
Hollow fiber means a hollow structure having a tubular shape in the axial direction of the fiber, and the hollow structure makes the fiber itself light in weight, breathable and elastic, and is widely used in various fields such as clothing, sports and industry.
The surface of the hollow fiber contains hydrophilic groups of macromolecular chains and micro holes, the hydrophilic groups are combined with water molecules to achieve the water absorption effect, the micro holes absorb the water molecules through the surface effect to achieve the water absorption effect, but the water absorption capacity of the water absorption mode is very limited, and the water retention of the fiber is poor under the action of pressure.
Therefore, there is a need to provide an absorbable hollow fiber which is excellent in both water absorbency and water retention.
Disclosure of Invention
In order to solve the problems of limited water absorption capacity and poor water retention of the hollow fiber. The present application provides an absorbable hollow fiber.
In a first aspect, the present application provides an absorbable hollow fiber, which adopts the following technical scheme:
The absorbable hollow fiber comprises, by weight, 6-12 parts of sodium alginate modified starch, 3-9 parts of gelatin and 2-8 parts of nano silver microcapsules.
By adopting the technical scheme, a large number of carboxyl and hydroxyl functional groups exist in the sodium alginate modified starch structure, the gelatin is a polydisperse system with certain molecular weight distribution, gelatin molecular chains are mutually connected to form a compact and uniform network structure, the sodium alginate modified starch is dispersed in gaps of the network structure to present a mosaic filling state, a compact and compact crosslinking structure is formed, the cohesiveness and the water absorbability of the gelatin are further improved, and the water retention of the gelatin is further improved; the nano silver microcapsule has a bactericidal effect, and the nano silver microcapsule is dispersed into a network structure of gelatin molecules, and the sodium alginate modified starch further promotes the cohesiveness of the nano silver microcapsule and the gelatin molecules, so that the bactericidal performance of the prepared hollow fiber is durable.
Preferably, the preparation method of the sodium alginate modified starch comprises the following steps:
(1) Adding starch into deionized water to obtain a starch solution with the mass fraction of 10-20%, heating to 50-60 ℃, adding potassium permanganate, reacting for 10-20h, adding sodium hydroxide solution, stirring for 20-30min to terminate oxidation reaction, adding calcium chloride, and fully mixing to obtain a mixture I;
(2) And (3) performing ultrasonic treatment on the mixture obtained in the step (1) for 10-30min, adding sodium alginate, adding allyl alcohol glycidyl ether, heating to 70-80 ℃, preserving heat for 2-3h, adding ethanol, preserving heat for 1-3h, filtering, and drying to obtain sodium alginate modified starch.
By adopting the technical scheme, the oxidized starch contains aldehyde or carboxyl molecules, so that the initial adhesion of the starch can be improved, meanwhile, the aldehyde or carboxyl molecules can activate the adjacent starch molecules, the polymerization degree of the starch molecules can be reduced through oxidation, the molecular chain of the starch molecules is shortened, and the solubility, the adhesion and the water retention of the starch are further improved.
The sodium alginate structure contains a large number of hydroxyl and carboxyl, and sodium alginate is added to crosslink and modify the starch solution to form a three-dimensional reticular crosslinked structure, so that the adhesiveness and the water-retaining property of the starch solution are further improved; the addition of the calcium chloride not only increases the viscosity of the starch solution, but also can increase the viscosity of the sodium alginate, and the mixture of the sodium alginate and the calcium chloride forms a compact crosslinked network structure, so that the sodium alginate has excellent biocompatibility, biodegradability and bioadhesion, and is further beneficial to modifying the starch by the sodium alginate.
Because of the existence of a large number of carboxyl groups with strong hydration in the sodium alginate macromolecules, the sodium alginate has high Newton viscosity, lower structural viscosity and poorer rheological property, allyl alcohol glycidyl ether can further modify the sodium alginate, reactive double bonds are introduced into the molecular chain of the sodium alginate, the sodium alginate and starch are promoted to be crosslinked and modified, the rheological property and the cohesiveness of the sodium alginate are improved, and meanwhile, the modified starch has higher cohesiveness and water retention.
Preferably, the mass ratio of the starch to the calcium chloride to the sodium alginate is 1:0.8-1.5:1.2-2.5.
By adopting the technical scheme, the sodium alginate and the calcium chloride are crosslinked to form a closed network structure, and the sodium alginate is added into the starch for crosslinking modification to form a three-dimensional net-shaped crosslinked structure, so that the cohesiveness of the starch is further improved, and the water retention of the starch is effectively improved; the mass ratio of potato starch, calcium chloride and sodium alginate is controlled, and the sodium alginate modified starch with better water absorption, better viscosity and better water retention is obtained.
Preferably, the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is 1:0.4-0.8.
Through adopting the technical scheme, sodium alginate molecules contain a large number of hydroxyl and carboxyl, allyl alcohol glycidyl ether is a synthetic coupling agent, sodium alginate is modified by adopting allyl alcohol glycidyl ether, a double bond which is easy to react is introduced into the molecular structure of the sodium alginate, the crosslinking reaction of the sodium alginate and starch is promoted, the sodium alginate modified starch with a three-dimensional network structure is formed, the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is controlled, and the sodium alginate modified starch with better water absorption, better viscosity and better water retention is obtained.
Preferably, the nano silver microcapsule is prepared from a core material and a wall material with a mass ratio of 1:4-8; the core material comprises nano silver, zirconium phosphate, silicon dioxide and tea polyphenol; the wall material comprises glyceryl tristearate, chitosan and styrene.
By adopting the technical scheme, the nano silver takes zirconium phosphate as a carrier, has the advantages of high safety, good heat resistance and good chemical stability, has the characteristics of broad-spectrum antibiosis and lasting antibiosis, can kill and remove various bacteria in a high-efficiency broad-spectrum manner, the silicon dioxide has antibiosis performance and stronger dispersion effect, the zirconium phosphate and the silicon dioxide are matched for use, so that the probability of nano silver agglomeration is effectively reduced, the tea polyphenol is a natural antimicrobial agent, and has good safety and biodegradability, but due to poor heat resistance, the sterilization duration is short, the tea polyphenol is matched with the nano silver for use, the sterilization durability of the tea polyphenol is effectively improved, and the synergistic effect can be achieved.
The chitosan is a widely-existing natural polymer material, has biodegradability, is pollution-free to the environment, and utilizes chemical bond action to graft styrene on the surface of the chitosan, so that the adsorption effect of the chitosan is increased, the glyceryl tristearate and the chitosan not only have sterilization effect, but also are favorable for the structural stability of a chitosan system, and the prepared wall material can better embed the core material, so that the slow release effect of nano silver and tea polyphenol in the core material is improved, and the sterilization duration of the nano silver microcapsule is prolonged.
The nano silver, zirconium phosphate, silicon dioxide and tea polyphenol are embedded in a microcapsule structure, and the nano silver and the tea polyphenol can be slowly released through the embedding effect of the microcapsule, so that the lasting antibacterial effect is realized.
Preferably, the preparation method of the silver oxide microcapsule comprises the following steps:
(1) Mixing nano silver, zirconium phosphate and silicon dioxide, stirring at 80-90 ℃ at a stirring speed of 100-200r/min for 30-45min, adding tea polyphenol, and stirring to obtain a mixture I;
(2) Mixing glyceryl tristearate, chitosan and styrene, and stirring at 70-80deg.C for 10-35min to obtain a second mixture;
(3) Adding the mixture I obtained in the step (1) and the emulsifier into the mixture II obtained in the step (2), homogenizing for 8-12min under a homogenizer of 1500-2000r/min, adjusting the pH value to 3-4, freezing for 12-24h in a refrigerator of-10 to 80 ℃, and then drying for 24-48h in a freeze dryer to obtain the silver oxide microcapsule.
By adopting the technical scheme, the nano silver, zirconium phosphate and silicon dioxide are stirred at the temperature of 80-90 ℃, so that the nano silver can be well dispersed, the nano silver is stably loaded on the surfaces of the zirconium phosphate and the silicon dioxide, the glyceryl tristearate, the chitosan and the styrene are stirred at the temperature of 70-80 ℃, the structural stability of a wall material system is improved, and the subsequent embedding effect of the nano silver is facilitated.
Preferably, the mass ratio of the nano silver to the zirconium phosphate to the silicon dioxide is 1:1-3:0.5-0.8.
By adopting the technical scheme, zirconium phosphate can be used as a multifunctional mesoporous material and can be used as a carrier of nano silver, so that the antibacterial effect of the nano silver is durable, silicon dioxide can be used as a carrier of nano silver particles, has a dispersing effect, reduces aggregation of the nano silver particles, controls the mass ratio of the nano silver to the zirconium phosphate to the silicon dioxide, and is further beneficial to promoting the sterilizing function and antibacterial durability of the nano silver.
Preferably, the mass ratio of the glyceryl tristearate to the chitosan to the styrene is 3-6:1:0.5-1.5.
By adopting the technical scheme, after the chitosan is grafted by the styrene, the adsorption effect of the chitosan is increased, the addition of the glyceryl tristearate stabilizes the molecular structure of the chitosan, and the mass ratio of the glyceryl tristearate, the chitosan and the styrene is controlled, so that the nano silver microcapsule with better embedding effect is obtained.
In a second aspect, a method of making an absorbable hollow fiber, comprising the steps of:
S1, mixing sodium alginate modified starch, gelatin and nano silver microcapsules, adding dimethyl sulfoxide solvent to prepare 20-30% solution serving as outer tube spinning solution, injecting the outer tube of a coaxial spinneret, allowing a core material to enter the inner tube, and performing coaxial electrostatic spinning at room temperature to obtain fibers; the spinning parameters are as follows: the flow rate of the inner tube core material is 0.2-0.8mL/h, the flow rate of the outer tube solution is 0.8-1.2mL/h, the voltage is 15-25kV, and the receiving distance is 10-25cm. The inner/outer diameter of the inner tube of the coaxial spinneret is 0.5/0.7mm respectively, and the inner/outer diameter of the outer tube is 1.2/2mm respectively;
s2, soaking the fiber prepared in the step S1 in acetone, removing the core material, and drying to obtain the hollow fiber.
By adopting the technical scheme, the outer tube spinning solution comprises sodium alginate modified starch, gelatin and nano silver microcapsule mixed solution, and is matched with the inner tube core material, so that the hollow fiber obtained by spinning has higher liquid absorption capacity, water retention capacity and antibacterial durability, and the service performance of the hollow fiber is improved.
Preferably, the core material is mineral oil, vegetable oil, polyethylene glycol, glycerol and derivatives thereof, and air.
Through adopting above-mentioned technical scheme, the core adopts above-mentioned material to help getting rid of hollow fiber's inner core, obtains hollow fiber fast, and the raw materials is abundant, easy operation.
In summary, the application has the following beneficial effects:
1. The sodium alginate modified starch has stronger water absorption and adhesiveness, gelatin molecular chains are mutually connected to form a compact and uniform reticular structure, the sodium alginate modified starch is dispersed in gaps of the reticular structure to be in a inlaid and filled state, a compact and compact cross-linked structure is formed, the adhesiveness and the water absorption of gelatin are further improved, and the water retention of gelatin is further improved; the nano silver microcapsule has a bactericidal effect, and the nano silver microcapsule is dispersed into a network structure of gelatin molecules, and the sodium alginate modified starch further promotes the cohesiveness of the nano silver microcapsule and the gelatin molecules, so that the bactericidal performance of the prepared hollow fiber is durable.
2. According to the application, the sodium alginate is used for carrying out crosslinking modification on the starch solution to form a three-dimensional reticular crosslinking structure, so that the adhesiveness and the water-retaining property of the starch solution are improved; the addition of the calcium chloride not only increases the viscosity of the starch solution, but also can increase the viscosity of the sodium alginate, and the mixture of the sodium alginate and the calcium chloride forms a compact crosslinked network structure, so that the sodium alginate has excellent biocompatibility, biodegradability and bioadhesion, and is further beneficial to modifying the starch by the sodium alginate.
3. The sodium alginate macromolecule has a large number of carboxyl groups with strong hydration, so that the sodium alginate has high Newton viscosity, lower structural viscosity and poorer rheological property, the allyl alcohol glycidyl ether can further modify the sodium alginate, reactive double bonds are introduced into the molecular chain of the sodium alginate, the sodium alginate and starch are promoted to be crosslinked and modified, the rheological property and the cohesiveness of the sodium alginate are improved, and meanwhile, the modified starch has higher cohesiveness and water retention.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example of sodium alginate modified starch
PREPARATION EXAMPLE 1-1
The preparation method of the sodium alginate modified starch comprises the following steps:
(1) Adding 15kg of potato starch into 100L of deionized water to obtain a starch solution with the mass fraction of 15%, heating to 55 ℃, adding 0.02kg of potassium permanganate, reacting for 15 hours, adding 10kg of sodium hydroxide solution with the mass fraction of 8%, stirring for 25 minutes to terminate the oxidation reaction, adding calcium chloride, and fully mixing to obtain a mixture I;
(2) Performing ultrasonic treatment on the mixture obtained in the step (1) for 20min, adding sodium alginate, adding allyl alcohol glycidyl ether, heating to 75 ℃, preserving heat for 2h, adding 600L of ethanol, preserving heat for 2h, filtering, and drying to obtain sodium alginate modified starch; wherein the mass ratio of potato starch to calcium chloride to sodium alginate is 1:1.2:2; the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is 1:0.6.
PREPARATION EXAMPLES 1-2
The preparation method of the sodium alginate modified starch comprises the following steps:
(1) Adding 20kg of potato starch into 200L of deionized water to obtain a starch solution with the mass fraction of 10%, heating to 60 ℃, adding 0.04kg of potassium permanganate, reacting for 20h, adding 20kg of a sodium hydroxide solution with the mass fraction of 5%, stirring for 30min to terminate the oxidation reaction, adding calcium chloride, and fully mixing to obtain a mixture I;
(2) Performing ultrasonic treatment on the mixture obtained in the step (1) for 30min, adding sodium alginate, adding allyl alcohol glycidyl ether, heating to 80 ℃, preserving heat for 3h, adding 700L of ethanol, preserving heat for 3h, filtering, and drying to obtain sodium alginate modified starch; wherein the mass ratio of potato starch to calcium chloride to sodium alginate is 1:0.8:1.2; the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is 1:0.4.
Preparation examples 1 to 3
The preparation method of the sodium alginate modified starch comprises the following steps:
(1) Adding 20kg of potato starch into 100L of deionized water to obtain a starch solution with the mass fraction of 20%, heating to 50 ℃, adding 0.01kg of potassium permanganate, reacting for 10 hours, adding 12kg of a sodium hydroxide solution with the mass fraction of 10%, stirring for 20 minutes to terminate the oxidation reaction, adding calcium chloride, and fully mixing to obtain a mixture I;
(2) Performing ultrasonic treatment on the mixture obtained in the step (1) for 10min, adding sodium alginate, adding allyl alcohol glycidyl ether, heating to 70 ℃, preserving heat for 2h, adding 500L of ethanol, preserving heat for 1h, filtering, and drying to obtain sodium alginate modified starch; wherein the mass ratio of potato starch to calcium chloride to sodium alginate is 1:0.8:2.5; the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is 1:0.8.
Preparation examples 1 to 4
The difference from preparation example 1-1 is that calcium chloride was not added in step (1).
Preparation examples 1 to 5
The difference from preparation example 1-1 is that allyl alcohol glycidyl ether was not added in step (2).
Preparation examples 1 to 6
The difference from preparation example 1-1 is that the mass ratio of starch, calcium chloride and sodium alginate is 1:0.4:0.8.
Preparation examples 1 to 7
The difference from preparation example 1-1 is that the mass ratio of starch, calcium chloride and sodium alginate is 1:1.9:2.9.
Preparation examples 1 to 8
The difference from preparation example 1-1 is that the mass ratio of sodium alginate to allyl alcohol glycidyl ether is 1:0.2.
Preparation examples 1 to 9
The difference from preparation example 1-1 is that the mass ratio of sodium alginate to allyl alcohol glycidyl ether is 1:1.2.
Preparation example of nano silver microcapsule
PREPARATION EXAMPLE 2-1
The nano silver microcapsule is prepared from a core material and a wall material in a mass ratio of 1:6; the core material comprises nano silver, zirconium phosphate, silicon dioxide and tea polyphenol; the wall material comprises glyceryl tristearate, chitosan and styrene.
The preparation method of the silver oxide microcapsule comprises the following steps:
(1) Mixing 10kg of nano silver, zirconium phosphate and silicon dioxide, stirring at a temperature of 85 ℃ at a stirring speed of 150r/min for 35min, adding 5kg of tea polyphenol, and stirring to obtain a mixture I; wherein the mass ratio of the nano silver to the zirconium phosphate to the silicon dioxide is 1:2:0.6.
(2) Mixing 20kg of glyceryl tristearate, chitosan and styrene, and stirring at 75 ℃ for 25min to obtain a mixture II; wherein the mass ratio of the glyceryl tristearate to the chitosan to the styrene is 4:1:0.9.
(3) Adding the mixture I obtained in the step (1) and 2kg of glycerin fatty acid ester into the mixture II obtained in the step (2), homogenizing for 10min under a 1800r/min homogenizer, adjusting the pH to 3, freezing for 18h in a refrigerator with the temperature of-10 to 80 ℃, and then drying for 29h in a freeze dryer to obtain the silver oxide microcapsule.
PREPARATION EXAMPLE 2-2
The nano silver microcapsule is prepared from a core material and a wall material in a mass ratio of 1:4; the core material comprises nano silver, zirconium phosphate, silicon dioxide and tea polyphenol; the wall material comprises glyceryl tristearate, chitosan and styrene.
The preparation method of the silver oxide microcapsule comprises the following steps:
(1) Mixing 10kg of nano silver, zirconium phosphate and silicon dioxide, stirring at 90 ℃ at a stirring speed of 100r/min for 45min, adding 6kg of tea polyphenol, and stirring to obtain a mixture I; wherein the mass ratio of the nano silver to the zirconium phosphate to the silicon dioxide is 1:1:0.5.
(2) Mixing 20kg of glyceryl tristearate, chitosan and styrene, and stirring at 80 ℃ for 10min to obtain a mixture II; wherein the mass ratio of the glyceryl tristearate to the chitosan to the styrene is 3:1:1.5.
(3) Adding the mixture I obtained in the step (1) and 2.5kg of glycerin fatty acid ester into the mixture II obtained in the step (2), homogenizing for 12min under a 1500r/min homogenizer, adjusting the pH to 3, freezing for 24h in a refrigerator at-10 to 80 ℃, and then drying for 48h in a freeze dryer to obtain the silver oxide microcapsule.
PREPARATION EXAMPLES 2-3
The nano silver microcapsule is prepared from a core material and a wall material in a mass ratio of 1:8; the core material comprises nano silver, zirconium phosphate, silicon dioxide and tea polyphenol; the wall material comprises glyceryl tristearate, chitosan and styrene.
The preparation method of the silver oxide microcapsule comprises the following steps:
(1) Mixing 10kg of nano silver, zirconium phosphate and silicon dioxide, stirring at the temperature of 80 ℃ at the stirring speed of 200r/min for 30min, then adding 4kg of tea polyphenol, and stirring to obtain a mixture I; wherein the mass ratio of the nano silver to the zirconium phosphate to the silicon dioxide is 1:3:0.8.
(2) Mixing 20kg of glyceryl tristearate, chitosan and styrene, and stirring at 70 ℃ for 35min to obtain a mixture II; wherein the mass ratio of the glyceryl tristearate to the chitosan to the styrene is 6:1:0.5.
(3) Adding the mixture I obtained in the step (1) and 3kg of glycerin fatty acid ester into the mixture II obtained in the step (2), homogenizing for 8min under a homogenizer of 2000r/min, regulating the pH to 4, freezing for 12h in a refrigerator of-10 to 80 ℃, and then drying for 24h in a freeze dryer to obtain the silver oxide microcapsule.
PREPARATION EXAMPLES 2 to 4
The difference from preparation example 2-1 is that tea polyphenol is not added in step (1).
PREPARATION EXAMPLES 2 to 5
The difference from preparation example 2-1 is that chitosan was not added in step (2).
Preparation examples 2 to 6
The difference from preparation example 2-1 is that the mass ratio of nano silver, zirconium phosphate and silicon dioxide is 1:0.5:0.2.
Preparation examples 2 to 7
The difference from preparation example 2-1 is that the mass ratio of nano silver, zirconium phosphate and silicon dioxide is 1:3.5:1.2.
Preparation examples 2 to 8
The difference from preparation example 2-1 is that the mass ratio of glyceryl tristearate, chitosan and styrene is 2:1:0.2.
Preparation examples 2 to 9
The difference from preparation example 2-1 is that the mass ratio of glyceryl tristearate, chitosan and styrene is 8:1:1.8.
Examples
Example 1
The absorbable hollow fiber comprises the following components in parts by weight, 9kg of sodium alginate modified starch, 7kg of gelatin and 5kg of nano silver microcapsule; sodium alginate modified starch is prepared by adopting a preparation example 1-1, and nano silver microcapsules are prepared by adopting a preparation example 2-1;
a method of making an absorbable hollow fiber comprising the steps of:
S1, mixing sodium alginate modified starch, gelatin and nano silver microcapsules, adding dimethyl sulfoxide solvent to prepare 20% solution serving as outer tube spinning solution, injecting the outer tube of a coaxial spinneret, introducing soybean oil into the inner tube, and performing coaxial electrostatic spinning at room temperature to obtain fibers; the spinning parameters are as follows: the flow rate of soybean oil in the inner tube is 0.6mL/h, the flow rate of solution in the outer tube is 1.2mL/h, the voltage is 20kV, and the receiving distance is 15cm. The inner/outer diameter of the inner tube of the coaxial spinneret is 0.5/0.7mm respectively, and the inner/outer diameter of the outer tube is 1.2/2mm respectively;
s2, soaking the fiber prepared in the step S1 in acetone, removing the core material, and drying to obtain the hollow fiber.
Example 2
The difference with the embodiment 1 is that the absorbable hollow fiber comprises the following components in parts by weight, 6kg of sodium alginate modified starch, 3kg of gelatin and 8kg of nano silver microcapsule.
Example 3
The difference from example 1 is that an absorbable hollow fiber comprises the following components in parts by weight, 12kg of sodium alginate modified starch, 9kg of gelatin and 2kg of nano silver microcapsule.
Example 4
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-2.
Example 5
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-3.
Example 6
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-4.
Example 7
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-5.
Example 8
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-6.
Example 9
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-7.
Example 10
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-8.
Example 11
The difference from example 1 is that sodium alginate modified starch was prepared using preparation examples 1-9.
Example 12
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2-2.
Example 13
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2-3.
Example 14
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2 to 4.
Example 15
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2 to 5.
Example 16
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2 to 6.
Example 17
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2 to 7.
Example 18
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2 to 8.
Example 19
The difference from example 1 is that nano silver microcapsules were prepared using preparation examples 2 to 9.
Comparative example
Comparative example 1
The absorbable hollow fiber comprises the following components in parts by weight, 15kg of sodium alginate modified starch, 13 kg kg of gelatin and 1kg of nano silver microcapsule.
Comparative example 2
The absorbable hollow fiber comprises the following components in parts by weight, 4kg of sodium alginate modified starch, 2kg of gelatin and 10kg of nano silver microcapsule.
Comparative example 3
The difference from example 1 is that the sodium alginate modified starch is replaced by an equivalent amount of potato starch.
Comparative example 4
The difference from example 1 is that the sodium alginate modified starch is replaced by an equivalent amount of gelatin.
Comparative example 5
The difference from example 1 is that the nano-silver microcapsules are replaced by an equal amount of gelatin.
Comparative example 6
The difference from example 1 is that the gelatin is replaced by an equivalent amount of sodium alginate modified starch.
Performance test
Detection method/test method
1. Water absorption test: weighing 10g of sample, adding 100L of deionized water, standing on a screen for 3min after water absorption saturation until no free water drops, weighing the mass of the screen and the sample after water absorption, and calculating the water absorption multiple (expressed by WRV) according to the following formula; WRV (g/g) = (W) 1-W2)/W3
Wherein: w 1 is the mass of the gel after sieving and water absorption, g;
w 2 is the mass of the sieve, g;
w 3 is the mass of the sample before water absorption, g;
2. Water retention test: (a) ability to retain water in a natural state: 10g of sample is weighed, 100L of deionized water is added, after water absorption is saturated, standing is carried out, the water absorption multiple of the sample is measured, then the water absorption sample is put into a beaker for standing, the weights of the beaker and gel are weighed once a week, and the water content of the resin is calculated.
(B) Pressurized water retention test: weighing 10g of sample, adding 100L of deionized water, standing after water absorption saturation, measuring the water absorption multiple of the sample, placing a round glass plate with the diameter of 9.8cm in a sample separating sieve containing the sample, placing weights on the plate, weighing the sieve and the water absorption gel every 1h, and obtaining the water content of the pressurized water absorption gel.
3. Sterilization test: the staphylococcus aureus is used as an antibacterial test, the culture medium is nutrient gravy agar, samples with the same size and shape are placed in a culture set, the staphylococcus aureus is inoculated, the concentration is 10 9 CFU/mL, and the antibacterial rates of 0h, 48h and 72h are calculated respectively.
TABLE 1
As can be seen from Table 1, the absorbable hollow fiber prepared by the application has strong water absorption, adhesion and water retention, and has durable sterilization performance. The hollow fiber prepared in the examples 1-5 has water absorption multiple as high as 1200 or more, and the water retention capacity is basically unchanged after 24 hours under the natural state, and still has higher water retention capacity after 72 hours and is kept around 1200; the water retention capacity under pressure is kept at about 1200 hours, and still has higher water retention capacity after 72 hours and is kept at about 1180; the antibacterial rate of the prepared hollow fiber is up to 99.9%, and the antibacterial rate of the fiber is continuously detected after 72 hours and is kept about 99.6%, which shows that the prepared hollow fiber has better antibacterial durability.
In example 6, calcium chloride is not added in the preparation process of the sodium alginate modified starch, and as can be seen from table 1, the water absorption multiple of the prepared hollow fiber is 1100, the water retention performance under the natural state is 1045 after 72 hours; water retention capacity under pressure, after 72h at 1023; the addition of the calcium chloride is shown to influence the water absorbability and the water retention property of the hollow fiber, the calcium chloride can increase the viscosity of the sodium alginate, and the mixture of the sodium alginate and the calcium chloride forms a compact crosslinked network structure, so that the sodium alginate has excellent biocompatibility, biodegradability and bioadhesion, and is further beneficial to modifying the starch with the sodium alginate. The antibacterial rate of the prepared hollow fiber is up to 99.9%, and the antibacterial rate of the fiber is continuously detected after 72 hours and is kept at 99.7%, which shows that the prepared hollow fiber still has better sterilization durability.
In example 7, allyl alcohol glycidyl ether is not added in the preparation process of sodium alginate modified starch, and as can be seen from table 1, the water absorption multiple of the prepared hollow fiber is 1000, the water retention performance under the natural state is 943, and the water retention capacity after 72 hours is 943; water retention under pressure, after 72h at 911; the addition of allyl alcohol glycidyl ether is shown to influence the water absorption and water retention of the hollow fiber, the allyl alcohol glycidyl ether can further modify sodium alginate, reactive double bonds are introduced into the molecular chain of the sodium alginate, the sodium alginate and starch are promoted to be crosslinked and modified, the rheological property and the cohesiveness of the sodium alginate are improved, and meanwhile, the modified starch has higher cohesiveness and water retention. The antibacterial rate of the prepared hollow fiber is up to 99.9%, and the antibacterial rate of the fiber is continuously detected after 72 hours and is kept at 99.7%, which shows that the prepared hollow fiber still has better sterilization durability.
Examples 8 to 9 the mass ratio of starch, calcium chloride and sodium alginate was adjusted, examples 10 to 11 the mass ratio of sodium alginate to allyl alcohol glycidyl ether was adjusted, and as seen from table 1, the water absorption multiple of the prepared hollow fiber was about 1190, the water retention property in a natural state was about 1145 after 72 hours; water retention capacity under pressure, after 72h, around 1110; the mass ratio of starch, calcium chloride and sodium alginate is changed, and the mass ratio of sodium alginate to allyl alcohol glycidyl ether is changed to influence the water absorption and water retention of the hollow fiber; the sodium alginate and the calcium chloride are crosslinked to form a closed network structure, and the sodium alginate is added into the starch for crosslinking modification to form a three-dimensional network crosslinked structure, so that the water-retaining property of the starch is effectively improved; controlling the mass ratio of potato starch, calcium chloride and sodium alginate to obtain sodium alginate modified starch with better water absorption, better viscosity and better water retention; sodium alginate is modified by allyl alcohol glycidyl ether, and easily-reacted double bonds are introduced into the molecular structure of the sodium alginate, so that the crosslinking reaction of the sodium alginate and starch is promoted, the three-dimensional sodium alginate modified starch with a net structure is formed, and the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is controlled, so that the sodium alginate modified starch with better water absorption, better viscosity and better water retention is obtained. In addition, the hollow fiber still has better sterilization durability.
The hollow fibers prepared in examples 12-19 have water absorption multiple as high as 1200 or more, and the water retention capacity in a natural state is basically unchanged after 24 hours, and still have higher water retention capacity after 72 hours and are kept at 1180 or so; the water retention capacity under pressure is still higher after 72 hours, and the water retention capacity is kept at about 1170; wherein, the antibacterial rate of the hollow fiber prepared in examples 12-13 is as high as 99.9%, and the antibacterial rate of the fiber is continuously detected after 72 hours.
According to the preparation method of the silver oxide microcapsule in the embodiment 14, tea polyphenol is not added, the antibacterial rate of the hollow fiber is as high as 97.1%, and the antibacterial rate of the detection fiber is 90.1% after 72 hours, so that the tea polyphenol is matched with nano silver for use, the sterilization durability of the tea polyphenol is effectively improved, and the synergistic effect can be achieved.
According to the preparation method of the silver oxide microcapsule in the embodiment 15, chitosan is not added, the antibacterial rate of the hollow fiber is up to 95.2%, and the antibacterial rate of the detection fiber is 88.5% after 72 hours, so that the chitosan has a bactericidal effect, and the glyceryl tristearate is favorable for the structural stability of a chitosan system, so that the prepared wall material can better embed the core material, the slow release effect of nano silver and tea polyphenol in the core material is improved, and the bactericidal duration of the nano silver microcapsule is prolonged.
Examples 16-17 changed the mass ratio of nano silver, zirconium phosphate and silicon dioxide, examples 18-19 changed the mass ratio of glyceryl tristearate, chitosan and styrene, and the antibacterial rate of the prepared hollow fiber was reduced, indicating that controlling the mass ratio of nano silver, zirconium phosphate and silicon dioxide was helpful for promoting the sterilizing function and antibacterial durability of nano silver. The mass ratio of the glyceryl tristearate, the chitosan and the styrene is controlled, so that the nano silver microcapsule with better embedding effect can be obtained.
Comparative examples 1-2 the water absorption capacity of the prepared hollow fiber was 1190 or so, and the water retention capacity after 72 hours was 1140 or so; water retention under pressure, after 72h, was maintained at around 1090; the bacteriostasis rate of the prepared hollow fiber is about 99.0%, and the bacteriostasis rate of the fiber is continuously detected after 72 hours and is kept at about 96%, which shows that the dosage of each component influences the water absorption, the water retention and the sterilization durability of the hollow fiber.
In comparative example 3, potato starch is used to replace sodium alginate modified starch, and as can be seen from table 1, the water absorption multiple of the prepared hollow fiber is 800, the water retention performance under the natural state is 741, and the water retention capacity after 72 hours is 741; water retention under pressure, water retention after 72h at 721; in comparative example 4, gelatin is used to replace sodium alginate modified starch, and as can be seen from table 1, the water absorption multiple of the prepared hollow fiber is 805, the water retention performance under natural state is 745 after 72 hours; water retention under pressure, after 72h at 723; the addition of the sodium alginate modified starch has the effects on the water absorption and water retention of the hollow fiber, the sodium alginate modified starch has stronger water absorption and adhesiveness, and the sodium alginate modified starch is dispersed in the gaps of the network structure, so that the adhesiveness and water absorption of the gelatin are improved, and the water retention of the gelatin is further improved. The antibacterial rate of the prepared hollow fiber is up to 97.9%, and the antibacterial rate of the fiber is 92.6% after 72 hours, which indicates that the sodium alginate modified starch further promotes the cohesiveness of the nano silver microcapsule and gelatin molecules, so that the sterilizing performance of the prepared hollow fiber is durable.
In comparative example 5, gelatin is used to replace nano silver microcapsule, as can be seen from table 1, the water absorption and water retention of the prepared hollow fiber are basically unchanged, but the antibacterial rate of the fiber is obviously reduced, the antibacterial rate is 76.4%, and after 72 hours, the antibacterial rate of the fiber is 60.4% continuously detected, which indicates that nano silver, zirconium phosphate, silicon dioxide and tea polyphenol are embedded in a microcapsule structure, and the nano silver and tea polyphenol can be slowly released through the embedding effect of the microcapsule, so that the lasting antibacterial effect is realized.
In comparative example 6, sodium alginate modified starch is used to replace gelatin, and as can be seen from table 1, the water absorption multiple of the prepared hollow fiber is 980, the water retention performance under the natural state is 921, and the water retention capacity after 72 hours is 921; water retention capacity under pressure, after 72h at 901; the gelatin is matched with sodium alginate modified starch, so that the cohesiveness and water absorbability of the gelatin are improved, and the water-retaining property of the gelatin is further improved. The bacteriostasis rate of the prepared hollow fiber is basically kept unchanged, and the prepared hollow fiber has excellent and durable bactericidal performance.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (7)
1. The absorbable hollow fiber is characterized by comprising, by weight, 6-12 parts of sodium alginate modified starch, 3-9 parts of gelatin and 2-8 parts of nano silver microcapsules;
The preparation method of the sodium alginate modified starch comprises the following steps:
(1) Adding starch into deionized water to obtain a starch solution with the mass fraction of 10-20%, heating to 50-60 ℃, adding potassium permanganate, reacting for 10-20h, adding sodium hydroxide solution, stirring for 20-30min to terminate oxidation reaction, adding calcium chloride, and fully mixing to obtain a mixture I;
(2) Performing ultrasonic treatment on the mixture obtained in the step (1) for 10-30min, adding sodium alginate, adding allyl alcohol glycidyl ether, heating to 70-80 ℃, preserving heat for 2-3h, adding ethanol, preserving heat for 1-3h, filtering, and drying to obtain sodium alginate modified starch;
The nano silver microcapsule is prepared from a core material and a wall material in a mass ratio of 1:4-8; the core material comprises nano silver, zirconium phosphate, silicon dioxide and tea polyphenol; the wall material comprises glyceryl tristearate, chitosan and styrene;
the preparation method of the nano silver microcapsule comprises the following steps:
(1) Mixing nano silver, zirconium phosphate and silicon dioxide, stirring at 80-90 ℃ at a stirring speed of 100-200r/min for 30-45min, adding tea polyphenol, and stirring to obtain a mixture I;
(2) Mixing glyceryl tristearate, chitosan and styrene, and stirring at 70-80deg.C for 10-35min to obtain a second mixture;
(3) Adding the mixture I obtained in the step (1) and the emulsifier into the mixture II obtained in the step (2), homogenizing for 8-12min under a homogenizer of 1500-2000r/min, adjusting the pH to 3-4, freezing for 12-24h in a refrigerator of-10 to 80 ℃, and then drying for 24-48h in a freeze dryer to obtain the nano silver microcapsule.
2. An absorbable hollow fiber according to claim 1, wherein: the mass ratio of the starch to the calcium chloride to the sodium alginate is 1:0.8-1.5:1.2-2.5.
3. An absorbable hollow fiber according to claim 1, wherein: the mass ratio of the sodium alginate to the allyl alcohol glycidyl ether is 1:0.4-0.8.
4. An absorbable hollow fiber according to claim 1, wherein the mass ratio of nano silver, zirconium phosphate and silicon dioxide is 1:1-3:0.5-0.8.
5. An absorbable hollow fiber according to claim 1, wherein: the mass ratio of the glyceryl tristearate to the chitosan to the styrene is 3-6:1:0.5-1.5.
6. A method of preparing an absorbable hollow fiber according to any one of claims 1-5, comprising the steps of:
S1, mixing sodium alginate modified starch, gelatin and nano silver microcapsules, adding dimethyl sulfoxide solvent to prepare 20-30% solution serving as outer tube spinning solution, injecting the outer tube of a coaxial spinneret, allowing a core material to enter the inner tube, and performing coaxial electrostatic spinning at room temperature to obtain fibers; the spinning parameters are as follows: the flow rate of the inner pipe core material is 0.2-0.8mL/h, the flow rate of the outer pipe solution is 0.8-1.2mL/h, the voltage is 15-25kV, and the receiving distance is 10-25cm; the inner/outer diameter of the inner tube of the coaxial spinneret is 0.5/0.7mm respectively, and the inner/outer diameter of the outer tube is 1.2/2mm respectively;
s2, soaking the fiber prepared in the step S1 in acetone, removing the core material, and drying to obtain the hollow fiber.
7. The method for producing an absorbable hollow fiber according to claim 6, wherein: the core material is mineral oil, vegetable oil, polyethylene glycol, glycerol, derivatives thereof and air.
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WO2017066975A1 (en) * | 2015-10-23 | 2017-04-27 | 揭东巴黎万株纱华纺织有限公司 | Process for preparing coloured flame retardant polyester fibre |
CN111671181A (en) * | 2020-06-04 | 2020-09-18 | 中国制浆造纸研究院有限公司 | Mask and preparation method thereof |
DE102019128630A1 (en) * | 2019-10-23 | 2021-04-29 | Shanghai Boling Man Cosmetic Co., Ltd. | BIODEGRADABLE ABSORPTION MATERIAL |
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CN105442092A (en) * | 2016-01-22 | 2016-03-30 | 青岛中腾生物技术有限公司 | Absorbable hollow fiber and preparation method thereof |
DE102019128630A1 (en) * | 2019-10-23 | 2021-04-29 | Shanghai Boling Man Cosmetic Co., Ltd. | BIODEGRADABLE ABSORPTION MATERIAL |
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