CN115365492A - Preparation of antibacterial and antistatic nano particles and antibacterial and antistatic polylactic acid material - Google Patents
Preparation of antibacterial and antistatic nano particles and antibacterial and antistatic polylactic acid material Download PDFInfo
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- CN115365492A CN115365492A CN202211115154.6A CN202211115154A CN115365492A CN 115365492 A CN115365492 A CN 115365492A CN 202211115154 A CN202211115154 A CN 202211115154A CN 115365492 A CN115365492 A CN 115365492A
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- antibacterial
- antistatic
- polylactic acid
- titanium dioxide
- silver
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 75
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 75
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 38
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 36
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000002074 melt spinning Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 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 description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011231 conductive filler Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 238000007747 plating Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002657 fibrous material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of antibacterial and antistatic nano particles and an antibacterial and antistatic polylactic acid material, and relates to the technical field of multifunctional polylactic acid fibers, wherein the multifunctional nano particles are prepared by adopting a silver plating method on the surface of titanium dioxide, and silver plating not only enhances the conductivity and antibacterial property of the nano particles, but also can better enhance the interface performance compared with other methods for preparing the multifunctional nano particles; in addition, the preparation method of the antibacterial antistatic nano particles is simple, can be carried out at room temperature, is beneficial to production and processing, breaks through the dark defect of the traditional carbon conductive filler, and has wider application prospect in the field of fiber materials.
Description
The technical field is as follows:
the invention relates to the technical field of multifunctional polylactic acid fibers, in particular to preparation of antibacterial and antistatic nano particles and an antibacterial and antistatic polylactic acid material.
The background art comprises the following steps:
polylactic acid is derived from renewable crops and is considered to be the most likely biobased material to replace petroleum-based polyesters. The polylactic acid fiber prepared by solution spinning or melt spinning with polylactic acid as a main raw material has good application prospect in the textile field. However, polylactic acid fiber has some disadvantages, such as strong hydrophobicity of polylactic acid, and easy generation of static electricity during use, which affects processing and use performance; in addition, in the current textile field, consumers are more pursuing the antibacterial health care function of fabrics, so that the antibacterial property is also an important aspect for improving the added value of polylactic acid.
In order to improve the antistatic property of polylactic acid fiber, it is widely studied to introduce carbon black series, high molecular type antistatic agent or conductive filler such as metal oxide into the polylactic acid matrix. But the carbon black and the carbon nano tube antistatic fiber have the outstanding defects that the product has single color and only can be black or dark gray; the high-molecular antistatic agent has poor stability, the antistatic property has stronger environmental dependence, and the antistatic property can slowly decline along with the prolonging of time.
The nano particles are used for improving the performance of the polylactic acid, and endowing the polylactic acid with functions of antibiosis and the like is a direction of research and development. In the prior art, the nano particles have high surface energy and high activity and are easy to agglomerate; and the compatibility of the nano particles and the polylactic acid is poor, so that the nano particles are not easy to be uniformly and well dispersed in the polylactic acid, and the action effect of the nano particles is influenced.
The invention content is as follows:
due to the poor antistatic and antibacterial properties of polylactic acid, the carbon black conductive material used in the prior art has the problem of influencing the color of the product, the polymer antistatic agent has the problems of poor stability and strong dependence on the environment, and the problems of easy agglomeration of nano particles and poor compatibility with polylactic acid. The invention aims to provide the sodium polyacrylate coated silver-plated nano titanium dioxide particles, the silver-plated nano titanium dioxide has antibacterial and antistatic functions, and the defect of deep color of the traditional carbon conductive filler is overcome. The sodium polyacrylate is a non-toxic, harmless and good-stability high-molecular material, contains a large number of hydrophilic groups, and molecular chains extend after being dissociated in water, so that the surface area of the sodium polyacrylate is increased, and the sodium polyacrylate shows the advantage of being used as a dispersing matrix. Therefore, the sodium polyacrylate is used for coating the nano particles, so that the antistatic property is improved, the dispersity of the nano particles and the compatibility of the nano particles and polylactic acid are improved, and the structural function integration is realized.
One of the purposes of the invention is to provide a preparation method of antibacterial and antistatic nano particles, which comprises the following steps:
(1) Preparation of nano titanium dioxide
Adding butyl titanate and absolute ethyl alcohol into a reaction kettle, uniformly stirring, adding a mixed solution of triethanolamine and water, stirring for reaction, after the reaction is finished, carrying out suction filtration, washing and drying to obtain the nano titanium dioxide particles.
(2) Preparation of chemical silvering nano titanium dioxide
Adding water, ammonia water and silver nitrate into the reaction kettle, and uniformly stirring to obtain a silver-ammonia solution; and adding the prepared nano titanium dioxide into the silver-ammonia solution, uniformly stirring, adding a reducing agent, stirring for reaction, filtering, washing and drying after the reaction is finished, thereby obtaining the chemical silver-plated nano titanium dioxide particles.
(3) Preparation of sodium polyacrylate coated silver-plated nano titanium dioxide
Adding the prepared chemical silver-plated nano titanium dioxide and absolute ethyl alcohol into a reaction kettle, uniformly stirring, adding a sodium polyacrylate solution, stirring and reacting the obtained mixed solution, and after the reaction is finished, centrifuging, filtering, washing and drying to obtain the sodium polyacrylate coated silver-plated nano titanium dioxide, namely the antibacterial antistatic nano particles.
In the step (1), the molar ratio of the butyl titanate to the absolute ethyl alcohol to the water to the triethanolamine is 1; the reaction pH value is 8-12; the reaction temperature is room temperature, and the reaction time is 2-4 h.
In the step (2), the mass fraction of silver nitrate in the silver ammonia solution is 1-5%; the molar ratio of the ammonia water to the silver nitrate is 2:1-3:1; the pH value of the silver ammonia solution is 9-11; the mass fraction of the nano titanium dioxide in the silver ammonia solution is 10-20%; the reducing agent is at least one of glucose, formaldehyde and acetaldehyde, and the molar ratio of the reducing agent to the silver nitrate is 1:4-1:1; the reaction temperature is room temperature, and the reaction time is 2-4 h.
In the step (3), the mass fraction of the sodium polyacrylate solution is 5-20%, and the molecular weight of the sodium polyacrylate is 2000-15000; the mass fraction of the chemical silvering nano titanium dioxide in the mixed solution is 5-20%; the reaction temperature is room temperature, and the reaction time is 2-6 h.
The second purpose of the present invention is to provide antibacterial and antistatic nanoparticles obtained by the preparation method.
The invention also aims to provide an antibacterial and antistatic polylactic acid material, which comprises polylactic acid and the antibacterial and antistatic nano particles.
The mass ratio of the antibacterial antistatic nano particles to the polylactic acid is 1-10%, and preferably 2-6%.
The preparation method of the antibacterial and antistatic polylactic acid material comprises the steps of uniformly mixing polylactic acid and antibacterial and antistatic nano particles, adding the mixture into a double-screw extruder for melt blending, extruding and granulating to obtain antibacterial and antistatic polylactic acid particles, and then carrying out melt spinning to obtain the antibacterial and antistatic polylactic acid material.
The melt blending temperature is 170-190 ℃, and the screw rotating speed is 200-250rpm.
The melt spinning temperature is 220-245 ℃, and the spinning speed is 1000-3000m/min.
The invention has the beneficial effects that:
(1) The invention adopts the silver plating method on the surface of the titanium dioxide to prepare the multifunctional nano particles, and the silver plating not only enhances the conductivity and the antibacterial property of the nano particles, but also better enhances the interface performance compared with other methods for preparing the multifunctional nano particles.
(2) The sodium polyacrylate in the invention has the following functions: 1) High water absorption, which is helpful for improving antistatic performance; 2) The dispersion effect can inhibit the agglomeration of the nano particles; 3) As a high molecular compound, the sodium polyacrylate coated silver-plated nano titanium dioxide has good compatibility with polylactic acid, and improves the compatibility of nano particles and polylactic acid, so that the constructed sodium polyacrylate coated silver-plated nano titanium dioxide realizes structural function integration.
(3) The preparation method of the antibacterial antistatic nano particles is simple, can be carried out at room temperature, is beneficial to production and processing, breaks through the dark defect of the traditional carbon conductive filler, and has wider application prospect in the field of fiber materials.
(4) The invention uses few kinds of auxiliary agents, and solves the problem that the degradability of the polylactic acid is influenced by excessive kinds and addition of the auxiliary agents in the prior art.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
680g of butyl titanate and 460g of absolute ethyl alcohol are added into a reaction kettle, stirred for 20min, 298g of triethanolamine and 720g of water are uniformly mixed and then are dropwise added into a mixed solution of the butyl titanate and the absolute ethyl alcohol, and the mixture is stirred and reacted for 2h at room temperature. And (3) carrying out suction filtration, washing and drying on the white flocculent precipitate to obtain the nano titanium dioxide particles.
Adding 2kg of water, 9g of ammonia water and 20g of silver nitrate into the reaction kettle, and stirring for 20min to obtain a silver-ammonia solution; adding 200g of prepared nano titanium dioxide into the silver ammonia solution, continuing stirring for 20min, then adding 6g of acetaldehyde into the mixed solution, and stirring for reacting for 2h. After the reaction is finished, the chemical silver-plated nano titanium dioxide particles are obtained through suction filtration, washing and drying.
Adding 200g of prepared chemical silvering nano titanium dioxide and 500g of ethanol into a reaction kettle, and uniformly stirring; 200g of sodium polyacrylate with molecular weight of 2000 and 1800g of water are evenly mixed and slowly added into the silver-plated nano titanium dioxide solution, and the mixture is stirred and reacts for 2 hours. After the reaction is finished, the silver-plated nano titanium dioxide particles coated with the sodium polyacrylate and having the particle size of about 60nm are obtained through centrifugation, suction filtration, washing and drying.
And uniformly mixing 25g of prepared sodium polyacrylate coated silver-plated nano titanium dioxide particles with 2.5kg of polylactic acid, adding the mixture into a double-screw extruder, melting and blending at 180 ℃ at a rotating speed of 250rpm, and extruding and granulating to obtain the antibacterial and antistatic polylactic acid granules.
And (3) carrying out melt spinning on the prepared antibacterial and antistatic polylactic acid particles at 220 ℃, wherein the spinning speed is 1000m/min, so as to obtain the antibacterial and antistatic polylactic acid fiber.
Example 2
680g of butyl titanate and 460g of absolute ethyl alcohol are added into the reaction kettle, and stirred for 20min; 149g of triethanolamine and 900g of water are uniformly mixed and then are dropwise added into the mixed solution of the butyl titanate and the absolute ethyl alcohol, and the mixture is stirred and reacts for 3 hours at room temperature. And (4) carrying out suction filtration, washing and drying on the white flocculent precipitate to obtain the nano titanium dioxide particles.
Adding 2kg of water, 45g of ammonia water and 100g of silver nitrate into a reaction kettle, and stirring for 30min to obtain a silver-ammonia solution; adding 300g of prepared nano titanium dioxide into the silver ammonia solution, continuing stirring for 20min, then adding 12g of formaldehyde into the mixed solution, and stirring for reacting for 3h. After the reaction is finished, the chemical silver-plated nano titanium dioxide particles are obtained through suction filtration, washing and drying.
Adding 100g of prepared chemical silvering nano titanium dioxide and 200g of ethanol into a reaction kettle, stirring uniformly, mixing 100g of sodium polyacrylate with the molecular weight of 15000 and 1800g of water uniformly, slowly adding into the silvering nano titanium dioxide solution, and stirring for reacting for 2h. After the reaction is finished, the silver-plated nano titanium dioxide particles coated with the sodium polyacrylate with the particle size of about 70nm are obtained through centrifugation, suction filtration, washing and drying.
And (3) uniformly mixing 50g of prepared sodium polyacrylate coated silver-plated nano titanium dioxide particles with 2.5kg of polylactic acid, adding the mixture into a double-screw extruder, melting and blending at the temperature of 170 ℃ at the rotating speed of 200rpm, and extruding and granulating to obtain the antibacterial and antistatic polylactic acid granules.
And (3) carrying out melt spinning on the prepared antibacterial and antistatic polylactic acid particles at 230 ℃, wherein the spinning speed is 2000m/min, so as to obtain the antibacterial and antistatic polylactic acid fiber.
Example 3
680g of butyl titanate and 460g of absolute ethyl alcohol are added into the reaction kettle, and stirred for 20min; and then 149g of triethanolamine and 720g of water are uniformly mixed and then are dropwise added into the mixed solution of butyl titanate and absolute ethyl alcohol, and the mixture is stirred and reacts for 4 hours at room temperature. And (3) carrying out suction filtration, washing and drying on the white flocculent precipitate to obtain the nano titanium dioxide particles.
Adding 2kg of water, 24g of ammonia water and 50g of silver nitrate into a reaction kettle, and stirring for 30min to obtain a silver-ammonia solution; 300g of prepared nano titanium dioxide is added into the silver ammonia solution, stirring is continued for 30min, and then 50g of glucose is added into the mixed solution, and stirring reaction is carried out for 4h. After the reaction is finished, the chemical silver-plated nano titanium dioxide particles are obtained through suction filtration, washing and drying.
Adding 200g of prepared chemical silvered nano titanium dioxide and 600g of ethanol into a reaction kettle, and uniformly stirring; 200g of sodium polyacrylate with molecular weight of 8000 and 2kg of water are uniformly mixed and slowly added into the silver-plated nano titanium dioxide solution, and the mixture is stirred and reacted for 4 hours. After the reaction is finished, the silver-plated nano titanium dioxide particles coated with the sodium polyacrylate and having the particle size of about 40nm are obtained through centrifugation, suction filtration, washing and drying.
100g of prepared sodium polyacrylate coated silver-plated nano titanium dioxide particles and 2.5kg of polylactic acid are uniformly mixed, then the mixture is added into a double-screw extruder to be melted and blended at 180 ℃ and the rotating speed of 200rpm, and extrusion granulation is carried out to obtain the antibacterial and antistatic polylactic acid material.
And (3) carrying out melt spinning on the prepared antibacterial and antistatic polylactic acid particles at 245 ℃, wherein the spinning speed is 3000m/min, so as to obtain the antibacterial and antistatic polylactic acid fiber.
Example 4
Referring to example 3, except that the amount of the sodium polyacrylate coated silver-plated nano titanium dioxide particles is replaced by 6% of polylactic acid, and the antibacterial and antistatic polylactic acid particles are obtained by melt extrusion granulation.
And (3) carrying out melt spinning on the prepared antibacterial and antistatic polylactic acid particles at the temperature of 240 ℃, wherein the spinning speed is 2500m/min, so as to obtain the antibacterial and antistatic polylactic acid fiber.
Example 5
Referring to example 3, except that the amount of the sodium polyacrylate coated silver-plated nano titanium dioxide particles is replaced by 8% of polylactic acid, and the antibacterial and antistatic polylactic acid particles are obtained by melt extrusion granulation.
And (3) carrying out melt spinning on the prepared antibacterial and antistatic polylactic acid particles at the temperature of 240 ℃, wherein the spinning speed is 3000m/min, so as to obtain the antibacterial and antistatic polylactic acid fiber.
Example 6
Referring to example 3, except that the amount of the sodium polyacrylate coated silver-plated nano titanium dioxide particles was changed to 10% of the polylactic acid, and the antibacterial and antistatic polylactic acid particles were obtained by melt extrusion granulation.
And (3) carrying out melt spinning on the prepared antibacterial and antistatic polylactic acid particles at 230 ℃, wherein the spinning speed is 2000m/min, so as to obtain the antibacterial and antistatic polylactic acid fiber.
Comparative example 1
Referring to example 3, the silver-coated nano titanium dioxide particles coated with sodium polyacrylate were replaced with nano titanium dioxide particles, i.e., chemical silver coating and sodium polyacrylate coating were not performed.
Comparative example 2
Referring to example 3, sodium polyacrylate coated silver-plated nano titanium dioxide particles were replaced with chemically plated nano titanium dioxide particles, i.e., sodium polyacrylate coating was not performed.
Comparative example 3
Referring to example 3, polylactic acid fiber was prepared except that the untreated polylactic acid was directly used.
And (3) performance testing:
and (3) testing antibacterial performance: according to GB/T20944-2008, evaluation part 3 of antibacterial performance of textiles: and (3) measuring the bacteriostasis rate of the polylactic acid fiber to escherichia coli and staphylococcus aureus by an oscillation method.
And (3) resistivity testing: and testing the resistivity of the polylactic acid fiber by using an XR-1A fiber specific resistance tester.
Table 1 shows the antibacterial properties and antistatic properties of the polylactic acid fibers obtained in examples 1 to 6 and comparative examples 1 to 3.
TABLE 1
As can be seen from Table 1, the polylactic acid material without functional modification has poor antibacterial performance and high resistivity. From the viewpoint of antibacterial effect: after only 1% of sodium polyacrylate is added to coat the silver-plated nano titanium dioxide, the antibacterial rate of the silver-plated nano titanium dioxide to escherichia coli is 95.7% through detection, the antibacterial rate of the silver-plated nano titanium dioxide to staphylococcus aureus is 93.2%, and the antibacterial effect is obvious at a low addition level; when the addition amount of the sodium polyacrylate coated silver-plated nano titanium dioxide is increased to more than 2%, the bacteriostatic rate of the functionally modified polylactic acid reaches 99.99%. From the viewpoint of antistatic effect: when the addition amount is 1%, the resistivity is obviously reduced; the resistivity is less than 10 after the addition amount is increased to 2 percent 9 Omega.m, reaching the antistatic level. Compared with the comparative examples 2 and 3, the invention also shows that the organic combination of several functional materials plays an obvious role in synergism, can achieve ideal effects at a lower addition amount, does not influence the degradation of spinning and polylactic acid, and has wide application prospects in the field of functional polylactic acid.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the antibacterial antistatic nano particles is characterized by comprising the following steps:
(1) Preparation of nano titanium dioxide
Adding butyl titanate and absolute ethyl alcohol into a reaction kettle, uniformly stirring, adding a mixed solution of triethanolamine and water, stirring for reaction, and performing suction filtration, washing and drying to obtain nano titanium dioxide particles after the reaction is finished;
(2) Preparation of chemical silvering nano titanium dioxide
Adding water, ammonia water and silver nitrate into the reaction kettle, and uniformly stirring to obtain a silver-ammonia solution; adding the prepared nano titanium dioxide into silver ammonia solution, stirring uniformly, then adding a reducing agent, stirring for reaction, after the reaction is finished, carrying out suction filtration, washing and drying to obtain chemical silver-plated nano titanium dioxide particles;
(3) Preparation of sodium polyacrylate coated silver-plated nano titanium dioxide
Adding the prepared chemical silver-plated nano titanium dioxide and absolute ethyl alcohol into a reaction kettle, uniformly stirring, adding a sodium polyacrylate solution, stirring and reacting the obtained mixed solution, and after the reaction is finished, centrifuging, filtering, washing and drying to obtain the sodium polyacrylate coated silver-plated nano titanium dioxide, namely the antibacterial antistatic nano particles.
2. The method of claim 1, wherein: in the step (1), the molar ratio of the butyl titanate to the absolute ethyl alcohol to the water to the triethanolamine is 1; the reaction pH value is 8-12; the reaction temperature is room temperature, and the reaction time is 2-4 h.
3. The method of claim 1, wherein: in the step (2), the mass fraction of silver nitrate in the silver ammonia solution is 1-5%; the molar ratio of the ammonia water to the silver nitrate is 2:1-3:1; the pH value of the silver ammonia solution is 9-11; the mass fraction of the nano titanium dioxide in the silver ammonia solution is 10-20%; the reducing agent is at least one of glucose, formaldehyde and acetaldehyde, and the molar ratio of the reducing agent to the silver nitrate is 1:4-1:1; the reaction temperature is room temperature, and the reaction time is 2-4 h.
4. The method of claim 1, wherein: in the step (3), the mass fraction of the sodium polyacrylate solution is 5-20%, and the molecular weight of the sodium polyacrylate is 2000-15000; the mass fraction of the chemical silvering nano titanium dioxide in the mixed solution is 5-20%; the reaction temperature is room temperature, and the reaction time is 2-6 h.
5. Antibacterial antistatic nanoparticles obtained by the preparation method according to any one of claims 1 to 4.
6. An antibacterial and antistatic polylactic acid material, comprising polylactic acid and the antibacterial and antistatic nanoparticles of claim 5.
7. The antibacterial antistatic polylactic acid material as claimed in claim 6, wherein: the mass ratio of the antibacterial antistatic nano particles to the polylactic acid is 1-10%, and preferably 2-6%.
8. The antibacterial antistatic polylactic acid material as claimed in claim 6, wherein: the preparation method of the antibacterial and antistatic polylactic acid material comprises the steps of uniformly mixing polylactic acid and antibacterial and antistatic nano particles, adding the mixture into a double-screw extruder for melt blending, extruding and granulating to obtain antibacterial and antistatic polylactic acid particles, and then carrying out melt spinning to obtain the antibacterial and antistatic polylactic acid material.
9. The antibacterial antistatic polylactic acid material as claimed in claim 8, wherein: the melt blending temperature is 170-190 ℃, and the screw rotating speed is 200-250rpm.
10. The antibacterial antistatic polylactic acid material according to claim 8, wherein: the melt spinning temperature is 220-245 ℃, and the spinning speed is 1000-3000m/min.
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