CN114134598A - Environment-friendly degradable antiviral air filtration nanofiber material and preparation method thereof - Google Patents
Environment-friendly degradable antiviral air filtration nanofiber material and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
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Abstract
本发明公开了一种环保可降解抗病毒空气过滤纳米纤维材料及其制备方法，包括以下步骤：将10％‑30％的50‑100nm抗病毒纳米粒子加入到含有表面活性剂的水溶液中进行超声分散；将30‑60％PBAT聚合物粉末加入到上述溶液中继续搅拌至均匀后，烘干得到初始底料；将30‑60％PHB聚合物粉末加入到上述粉粉体中，在高速搅拌混合均匀后，进行混熔；将混溶体通过螺杆挤出装置进行造粒，并过筛，得到颗粒在烘干后形成熔喷母粒；将熔喷母粒熔融纺丝，得到一种环保可降解的抗病毒空气过滤纳米纤维材料。可对高效捕获抑制杀灭空气中存在的多种病原菌、流感病毒及冠状病毒，抑制率可达到99.9％。
The invention discloses an environment-friendly and degradable antiviral air filtration nanofiber material and a preparation method thereof, comprising the following steps: adding 10%-30% of 50-100nm antiviral nanoparticles into an aqueous solution containing a surfactant for ultrasonication Disperse; add 30-60% PBAT polymer powder to the above solution and continue to stir until uniform, then dry to obtain the initial primer; add 30-60% PHB polymer powder to the above powder, stir and mix at high speed After homogenization, mixing and melting is carried out; the miscible body is granulated through a screw extrusion device, and sieved to obtain the particles, which are dried to form melt-blown masterbatches; melt-spun the melt-blown masterbatches to obtain an environmentally friendly and degradable product Antiviral Air Filtration Nanofiber Material. It can effectively capture, inhibit and kill various pathogenic bacteria, influenza viruses and coronaviruses existing in the air, and the inhibition rate can reach 99.9%.
Description
Technical Field
The invention relates to the technical field of environmental air purification, in particular to an environmentally-friendly degradable antiviral air filtration nanofiber material and a preparation method thereof.
Background
Patients with respiratory infectious diseases can transmit pathogens to other people through exhaled breath, sneezing, coughing, sputum, nasal discharge and the like, thereby causing great hidden troubles to the health of the masses. The space needs to be sterilized, disinfected and purified in various public places and in the house, wherein the most efficient method is to sterilize and disinfect the space by using an air purification and filtration method.
Therefore, the market needs to sharply increase high-efficiency multifunctional filtering materials, and various filtering materials which have the functions of sterilizing, removing dust and haze, removing harmful decoration residues, removing peculiar smells and the like are provided for air in the market at the present stage. However, the main base material of the existing material is a difficult-to-degrade material such as PP and the like, and the functions of killing, dust fall and peculiar smell removal are mostly antiviral functions obtained by surface modification at the later stage, and the functional structure of the material is easy to fall off and fail to saturate; meanwhile, the base materials are all hydrophobic structures which can not effectively trap viruses and bacteria in air, and further, because the size of the fiber filter material produced by the existing melt spinning technology can only stay at the micron level, the interception capability of the fiber filter material on particles of 0.1-0.3 mu m is weak, and the particles of the size are easy to carry viruses to penetrate through the filter layer, so that the filter layer is ineffective. Meanwhile, the filter screen becomes waste after being used, further treatment is needed, and the existing materials can cause a large amount of white garbage pollution.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the environment-friendly degradable antiviral air filtration nanofiber material and the preparation method thereof are provided.
The invention provides the following technical scheme: the preparation method of the environment-friendly degradable antiviral air filtration nanofiber material comprises the following steps:
s1, adding 10-30% of 50-100nm antiviral nano particles into an aqueous solution containing 0.5-1% of a surfactant for ultrasonic dispersion;
s2, adding PBAT polymer powder with the mass of 30-60% into the solution, continuously stirring the mixture evenly, and drying the mixture to obtain an initial bottom material A;
s3, further adding degradable synthetic polymer powder accounting for 30-60% of the mass of the initial primer A into the initial primer A, stirring at a high speed and mixing uniformly, and then carrying out mixing and melting at the temperature of 160-220 ℃;
s4, granulating the mixed solution through a screw extrusion device, and sieving the granulated mixed solution through a 200-mesh sieve, wherein the working temperature is 180-250 ℃, and the obtained granules form melt-blown master batches after being dried;
s5, melt-spinning the melt-blown masterbatch, wherein the melt-blown masterbatch is heated to form a melt, the temperature is raised to the final melt temperature of 180--1The temperature of the post heater is 180-250 ℃, the cooling blowing speed is 0.3-0.5m/s, the blowing temperature is 20-30 ℃, the one-roll speed is 800-1000m/min, the drafting multiplying factor after hot rolling is improved by 6-9 times compared with that of the master batch, and the environment-friendly degradable antiviral air filtration nanofiber material is obtained.
Further, the degradable synthetic high polymer is a composition of Polyhydroxybutyrate (PHB), Polyhydroxyvalerate (PHBV) and polylactic acid (PLA), wherein the composition is prepared by mixing polyhydroxybutyrate, polyhydroxyvalerate and polylactic acid in a mass ratio of (1: 1) - (10: 1): 10 are mixed to form a solid phase mixture.
The method is further characterized in that the adding sequence of the polymer PBAT and the degradable polymer is that PBAT is firstly added, the two polymers are compounded, and under the condition of controlled melt-blowing, due to the difference of the viscosity and the molecular weight of the polymers, the high molecular weight part of components are secondarily stretched, so that the nanoscale melt-blown fibers are generated.
Further, the molecular weight of the polymer PBAT is between 5 and 10 ten thousand.
Further, the molecular weight of the polyhydroxybutyrate is between 18 and 30 ten thousand.
Further, the temperature rise rate of the temperature programming process is 20-50 ℃ per minute.
Further, the surfactant is sodium dodecyl benzene sulfonate, sodium lauryl sulfate, polyoxyethylene nonyl phenyl ether and the like.
Further, the antiviral nano particles are one or more of nano copper, nano cuprous oxide or nano zinc oxide.
The invention also provides the environment-friendly degradable antiviral air filtration nanofiber material prepared by the method.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
1. the environment-friendly degradable antiviral air filtration nanofiber material provided by the invention contains a nano copper structure which can effectively kill viruses and bacteria; meanwhile, the adopted polymer has certain hydrophilicity, so that the capability of trapping and inactivating microorganisms is increased, and the killing capability on various pathogenic bacteria, influenza viruses and coronaviruses can reach more than 99.5 percent.
2. According to the preparation method of the environment-friendly degradable antiviral air filtration nanofiber material provided by the invention, the used raw materials are degradable polymers, are non-toxic and harmless, have stable structures in the using process, and can be efficiently degraded when needing to be treated.
3. According to the preparation method of the environment-friendly degradable antiviral air filtration nanofiber material provided by the invention, the prepared melt-blown fiber can reach a nanometer level, and particles with the particle size of 0.1-0.3 mu m can be effectively intercepted.
4. The environment-friendly degradable antiviral air filtration nanofiber material provided by the invention is simple in production process, environment-friendly and low in energy consumption; and the morphology of the composite material can be diversified by adjusting the parameters of melt-blowing.
5. The invention mainly distinguishes the preparation method from other antiviral fiber materials, does not need to add a surface modifier, the PBAT material is naturally fused with antiviral nano-particle copper, cuprous oxide and zinc oxide, the adding sequence of the polymer PBAT and the degradable polymer is required to be PBAT first, and through the compounding of the two polymers, under the condition of regulated melt-blowing, due to the difference of the viscosity and the molecular weight of the polymers, the high molecular weight part components are stretched for the second time, so that the nanoscale melt-blown fiber is generated, the technical bottleneck that only micron-level melt-blown fiber can be generated through melt-blowing in the prior art is broken through, the hydrophilicity is realized, the virus and bacteria can be captured more efficiently, and the degradable different components are added to synthesize high polymer to prepare the nanoscale melt-blown fiber, so that the preparation method has the advantages of environmental protection.
Drawings
Fig. 1 is a scanning electron microscope photograph of a nanofiber structure prepared by the method provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the environment-friendly degradable antiviral air filtration nanofiber material provided by the embodiment comprises the following steps:
s1, adding 10% of 50nm nano-copper into an aqueous solution containing 0.5% of sodium dodecyl benzene sulfonate for ultrasonic dispersion;
s2, adding PBAT polymer powder with the mass of 30% into the solution, continuously stirring the mixture until the mixture is uniform, and drying the mixture to obtain an initial bottom material A;
s3, adding degradable synthetic polymer powder accounting for 30 percent of the mass of the initial primer A into the initial primer A,
after being stirred and mixed evenly at a high speed, the mixture is melted and mixed, and the melting and mixing temperature is 160 ℃;
s4, granulating the mixed solution through a screw extrusion device, and sieving the granulated mixed solution through a 200-mesh sieve, wherein the working temperature is 250 ℃, and the obtained granules are dried to form melt-blown master batches;
s5, melt-spinning the melt-blown masterbatch, wherein the melt-blown masterbatch is heated to form a melt, the temperature is raised at a rate of 20 ℃ per minute during the temperature raising process to reach a final melt temperature of 180 ℃, and the shear rate at a spinneret orifice is 1500S-1The temperature of the post heater is 250 ℃, the cooling blowing speed is 0.3m/s, the blowing temperature is 20 ℃, the speed of one roller is 1000m/min, the drafting multiplying power after hot rolling is improved by 6 times compared with that of the master batch, and the environment-friendly degradable antiviral air filtration nanofiber material shown in figure 1 is prepared. The order of addition of the polymer PBAT and the degradable polymer must be PBAT first.
The degradable synthetic high polymer is a composition of Polyhydroxybutyrate (PHB), Polyhydroxyvalerate (PHBV) and polylactic acid (PLA), and the composition is a solid-phase mixture formed by mixing polyhydroxybutyrate, polyhydroxyvalerate and polylactic acid according to a mass ratio of 1:1: 5.
The molecular weight of the PBAT polymer adopted by the invention is between 5 and 10 ten thousand, and the molecular weight of the polyhydroxybutyrate is between 18 and 30 ten thousand.
Example 2
The preparation method of the environment-friendly degradable antiviral air filtration nanofiber material provided by the embodiment comprises the following steps:
s1, adding 20% of 80nm nano cuprous oxide into an aqueous solution containing 1% of nonylphenol polyoxyethylene ether for ultrasonic dispersion;
s2, adding 60% of PBAT polymer powder into the solution, continuously stirring the mixture evenly, and drying the mixture to obtain an initial bottom material A;
s3, further adding 45% of degradable synthetic polymer powder relative to the mass of the initial base material A into the initial base material A, stirring at a high speed, uniformly mixing, and then carrying out mixing and melting at the temperature of 200 ℃;
s4, granulating the mixed solution through a screw extrusion device, and sieving the granulated mixed solution through a 200-mesh sieve, wherein the working temperature is 180 ℃, and the obtained granules are dried to form melt-blown master batches;
s5, melt-spinning the melt-blown masterbatch, wherein the melt-blown masterbatch is heated to form a melt, the temperature is raised at a rate of 35 ℃ per minute during the temperature raising process to reach a final melt temperature of 200 ℃, and the shear rate at a spinneret orifice is 800S-1The temperature of the post heater is 210 ℃, the cooling blowing speed is 0.5m/s, the blowing temperature is 25 ℃, the speed of one roller is 800 m/min, the drafting multiplying power after hot rolling is improved by 7.5 times compared with that of the master batch, and the environment-friendly degradable antiviral air filtration nanofiber material is obtained.
The degradable synthetic high polymer is a composition of Polyhydroxybutyrate (PHB), Polyhydroxyvalerate (PHBV) and polylactic acid (PLA), wherein the composition is a solid-phase mixture formed by mixing polyhydroxybutyrate, polyhydroxyvalerate and polylactic acid according to a mass ratio of 1:5: 5. The order of addition of the polymer PBAT and the degradable polymer must be PBAT first.
The molecular weight of the PBAT polymer adopted by the invention is between 5 and 10 ten thousand, and the molecular weight of the polyhydroxybutyrate is between 18 and 30 ten thousand.
Example 3
The preparation method of the environment-friendly degradable antiviral air filtration nanofiber material provided by the embodiment comprises the following steps:
s1, adding 30% of 100nm nano zinc oxide powder into an aqueous solution containing 0.8% of sodium lauryl sulfate for ultrasonic dispersion;
s2, adding 40% of PBAT polymer powder into the solution, continuously stirring the mixture evenly, and drying the mixture to obtain an initial bottom material A;
s3, further adding 60% of degradable synthetic polymer powder relative to the mass of the initial primer A into the initial primer A,
after being stirred and mixed uniformly at a high speed, the mixture is melted and mixed, and the melting and mixing temperature is 220 ℃;
s4, granulating the mixed solution through a screw extrusion device, and sieving the granulated mixed solution through a 200-mesh sieve, wherein the working temperature is 200 ℃, and the obtained granules are dried to form melt-blown master batches;
s5, melt-spinning the melt-blown masterbatch, wherein the melt-blown masterbatch is heated to form a melt, the temperature is raised at a rate of 50 ℃ per minute during the temperature raising process, the final melt temperature is 230 ℃, and the shear rate at a spinneret orifice is 1000S-1And the temperature of the post heater is 180 ℃, the cooling blowing speed is 0.4m/s, the blowing temperature is 30 ℃, the speed of one roller is 900m/min, and the drafting multiplying power after hot rolling is improved by 9 times compared with that of the master batch, so that the environment-friendly degradable antiviral air filtration nanofiber material is obtained.
The degradable synthetic high polymer is a composition of Polyhydroxybutyrate (PHB), Polyhydroxyvalerate (PHBV) and polylactic acid (PLA), and the composition is a solid-phase mixture formed by mixing polyhydroxybutyrate, polyhydroxyvalerate and polylactic acid according to a mass ratio of 1:10: 5.
Further characterized in that the order of addition of the polymer PBAT and the degradable polymer must be PBAT first.
The molecular weight of the PBAT polymer adopted by the invention is between 5 and 10 ten thousand, and the molecular weight of the polyhydroxybutyrate is between 18 and 30 ten thousand.
The antibacterial performance of the antibacterial master batch prepared in the embodiments 1-3 is detected according to GB/T21510-.
TABLE 1
As those skilled in the art will appreciate, the present invention may be embodied in many other specific forms without departing from the spirit or scope thereof. Although embodiments of the present invention have been described, it is to be understood that the present invention should not be limited to those precise embodiments, and that various changes and modifications can be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the environment-friendly degradable antiviral air filtration nanofiber material is characterized by comprising the following steps of:
s1, adding 10-30% of 50-100nm antiviral nano particles into an aqueous solution containing 0.5-1% of a surfactant for ultrasonic dispersion;
s2, adding PBAT polymer powder with the mass of 30-60% into the solution, continuously stirring the mixture evenly, and drying the mixture to obtain an initial bottom material A;
s3, further adding degradable synthetic polymer powder accounting for 30-60% of the mass of the initial primer A into the initial primer A, stirring at a high speed and mixing uniformly, and then carrying out mixing and melting at the temperature of 160-220 ℃;
s4, granulating the mixed solution through a screw extrusion device, and sieving the granulated mixed solution through a 200-mesh sieve, wherein the working temperature is 180-250 ℃, and the obtained granules form melt-blown master batches after being dried;
s5, melt-spinning the melt-blown masterbatch, wherein the melt-blown masterbatch is heated to form a melt, the temperature is raised to the final melt temperature of 180--1The temperature of the post heater is 180-250 ℃, the cooling blowing speed is 0.3-0.5m/s, the blowing temperature is 20-30 ℃, the one-roll speed is 800-1000m/min, the drafting multiplying factor after hot rolling is improved by 6-9 times compared with that of the master batch, and the environment-friendly degradable antiviral air filtration nanofiber material is obtained.
2. The preparation method of the environment-friendly degradable antiviral air filtration nanofiber material as claimed in claim 1, wherein the degradable synthetic high polymer is a composition of polyhydroxybutyrate, polyhydroxyvalerate and polylactic acid, and the composition is a solid-phase mixture formed by mixing polyhydroxybutyrate, polyhydroxyvalerate and polylactic acid according to a mass ratio of 1: 1-10: 5.
3. The preparation method of the environment-friendly degradable antiviral air filtration nanofiber material as claimed in claim 1, wherein the adding sequence of the polymer PBAT and the degradable polymer is PBAT first, the two polymers are compounded, and under the controlled melt-blown condition, due to the difference of polymer viscosity and molecular weight, the high molecular weight part of the components are stretched for the second time, so as to generate the nanoscale melt-blown fiber.
4. The method for preparing environment-friendly degradable antiviral air filtration nanofiber material according to claim 1, wherein the molecular weight of the polymer PBAT is between 5 and 10 ten thousand.
5. The method for preparing environment-friendly degradable antiviral air filtration nanofiber material according to claim 2, wherein the molecular weight of polyhydroxybutyrate is between 18 and 30 ten thousand.
6. The method for preparing environment-friendly degradable antiviral air filtration nanofiber material according to claim 1, wherein the temperature raising rate of the temperature programming process is 20-50 ℃ per minute.
7. The method for preparing environment-friendly degradable antiviral air filtration nanofiber material as claimed in claim 1, wherein the surfactant is selected from sodium dodecyl benzene sulfonate, sodium lauryl sulfate, polyoxyethylene nonyl phenyl ether, etc.
8. The method for preparing the environment-friendly degradable antiviral air filtration nanofiber material as claimed in claim 1, wherein the antiviral nanoparticles are one or more of nano-copper, nano-cuprous oxide or nano-zinc oxide.
9. The environmentally-friendly degradable antiviral air filtration nanofiber material prepared by the method of any one of claims 1-8.
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2021
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| CN103668541A (en) * | 2012-09-19 | 2014-03-26 | 合肥杰事杰新材料股份有限公司 | Degradable fibers containing PBAT (poly(butylene adipate-co-terephthalate)) and preparation method thereof |
| US20190388816A1 (en) * | 2018-07-03 | 2019-12-26 | Qian Huang | Melt-Blown Non-Woven Filter Material |
| CN110257947A (en) * | 2019-06-03 | 2019-09-20 | 浙江尤夫科技工业有限公司 | A kind of antibacterial polyester industrial yarn and preparation method thereof |
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| CN113291002A (en) * | 2021-03-10 | 2021-08-24 | 广东茂业医疗科技有限公司 | Antibacterial and antiviral mask containing cuprous oxide |
| CN113186616A (en) * | 2021-07-01 | 2021-07-30 | 江苏恒力化纤股份有限公司 | Uvioresistant polyester industrial yarn and preparation method thereof |
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