CN114395861A - Nano silicon dioxide grafted halamine antibacterial melt-blown material and preparation method and application thereof - Google Patents
Nano silicon dioxide grafted halamine antibacterial melt-blown material and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides a nano silicon dioxide grafted halamine antibacterial melt-blown material and a preparation method and application thereof. The preparation method comprises the following steps: adding hydrophilic nano-silica into a mercaptosilane coupling agent solution, and reacting to obtain modified silica; bonding the modified nano silicon dioxide and the N-halamine precursor by using a photoinitiator to obtain silicon dioxide grafted N-halamine precursor powder; mixing the powder with melt-blown polypropylene resin according to a preset proportion, and adding the mixture into a melt-blowing machine for melt-blowing treatment to obtain a silicon dioxide grafted N-halamine melt-blown material; and soaking the melt-blown material in a sodium hypochlorite solution to obtain the nano silicon dioxide grafted N-halamine antibacterial melt-blown material. The antibacterial melt-blown material prepared by the invention has high antibacterial rate, high filterability, long antibacterial aging and long service life, and the antibacterial component can be repeatedly regenerated.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a silicon dioxide grafted halamine antibacterial melt-blown material and a preparation method and application thereof.
Background
Under the global background of influenza virus pandemics, medical masks become an essential product for daily life of people. As a core material of the medical mask, the polypropylene melt-blown material utilizes the three-dimensional disordered fiber structure to adsorb and block the invasion of external pathogens. However, because polypropylene has no bactericidal and antiviral effects, pathogens blocked on the mask still survive, and if the operation is not proper in the process of wearing the mask, the risk of infection to a human body is very easily caused; moreover, if the used mask is not properly disposed in time, a potential infection source is generated, and the life safety of other people is threatened. In recent five years, the production value of masks in China is gradually increased year by year, the occupation ratio of medical masks is also increased year by year, and the core material of the mainstream masks in the current market is still the electrostatic electret melt-blown material, so that the antibacterial medical melt-blown material has a huge market. At present, most of traditional antibacterial melt-blown materials have the problems of easy loss of antibacterial agents, high toxicity of the antibacterial agents, short antibacterial effect, short service life and the like, and the application of the traditional antibacterial melt-blown materials in the aspect of medical melt-blown materials is limited.
N-halamine is a high-efficiency broad-spectrum antibacterial agent containing one or more nitrogen atoms, has a high sterilization rate and is stable and long-acting, and active chlorine components with antibacterial effects can be repeatedly regenerated through chlorination treatment of a sodium hypochlorite solution. At present, researches on preparing an antibacterial material by grafting an N-halamine precursor containing double bonds to a polymer molecular chain by using a free radical initiator are more. However, the addition of a radical initiator may cause other side reactions in addition to the initiation of the intended graft product, such as lowering the molecular weight of the polymer and initiating polymerization of the functional monomer itself, which not only affects the processability of the polymer but also causes useless consumption of the functional monomer, and the radical initiator may eventually remain in the polymer material, causing potential safety problems if the polymer material is in direct contact with the human body.
The patent with the application number of CN202010711332.6 discloses an antibacterial polypropylene melt-blown material and a preparation method and application thereof, wherein polypropylene is used as a base material, 1-vinyl imidazole is used as an antibacterial monomer, the antibacterial monomer is grafted to the main chain of the polypropylene to form a polypropylene melt-blown material intermediate, and then the antibacterial polypropylene melt-blown material is obtained through amine halogenation. The method has the following disadvantages: the introduced 1-vinyl imidazole causes the odor of the material to be extremely large, and potential safety hazards exist; and halogen elements in nitrogen-halogen bonds in the five-membered ring of the common vinyl imidazole are not easy to release, so that the antibacterial effect of the vinyl imidazole antibacterial agent is poor.
In view of the above, there is a need to design an improved silica-grafted halamine antibacterial meltblown material, and a method for preparing the same and an application thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a silicon dioxide grafted halamine antibacterial melt-blown material and a preparation method and application thereof.
In order to realize the aim, the invention provides a preparation method of a nano silicon dioxide grafted halamine antibacterial melt-blown material, which comprises the following steps:
s1, preparing modified silicon dioxide: adding hydrophilic nano-silica into a mercaptosilane coupling agent solution prepared from isopropanol and water according to a preset proportion, and performing ultrasonic dispersion, heating reflux, centrifugal washing and drying to obtain modified silica;
s2, preparation of silicon dioxide grafted N-halamine precursor powder: uniformly mixing the modified nano-silica prepared in the step S1 with an N-halamine precursor and a photoinitiator, adding the mixture into absolute ethyl alcohol, treating the mixture for 2 to 4 hours by using ultraviolet light, and performing centrifugal washing and vacuum drying to obtain silicon dioxide grafted N-halamine precursor powder;
s3, preparing the silicon dioxide grafted N-halamine melt-blown material: mixing the nano silicon dioxide grafted N-halamine precursor powder prepared in the step S2 with melt-blown polypropylene resin according to a preset proportion, and adding the mixture into a melt-blown machine for melt-blowing treatment to obtain a silicon dioxide grafted N-halamine melt-blown material;
s4, preparing the silicon dioxide grafted N-halamine antibacterial melt-blown material: and (4) soaking the silicon dioxide grafted N-halamine melt-blown material prepared in the step (S3) in a sodium hypochlorite solution for 10-20min, and performing washing, drying, hot pressing and electret treatment to obtain the nano silicon dioxide grafted N-halamine antibacterial melt-blown material.
As a further improvement of the invention, the mass ratio of the nano-silica grafted N-halamine precursor powder to the melt-blown polypropylene resin in the step S3 is (2-5) to (80-100).
As a further improvement of the present invention, in step S4, the sodium hypochlorite solution is a solution diluted by 20-30 times by antipfurin, and 1 wt% of a surfactant and a pH adjuster are added to the sodium hypochlorite solution, and the pH of the sodium hypochlorite solution is 4-7.
As a further improvement of the present invention, the surfactant is triton; the pH regulator is dilute sulfuric acid.
As a further improvement of the invention, the mass ratio of the nano-silica to the mercaptosilane coupling agent in the step S1 is (8-12): 1-5, and the volume ratio of the isopropanol to the water is (2-5): 1.
As a further improvement of the invention, the N-halamine precursor in step S2 includes one of methacrylamide, 1-allylhydantoin, and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine.
As a further improvement of the invention, the mass ratio of the modified nano silicon dioxide to the N-halamine precursor in the step S2 is (8-12) to (3-6); the mass of the photoinitiator accounts for 0.1-0.5% of the total mass of the modified nano silicon dioxide and the N-halamine precursor; the photoinitiator is benzoin dimethyl ether.
As a further improvement of the invention, in step S3, the melt blowing machine comprises four heating sections, the temperature setting range is 180-240 ℃, the hot air temperature is 220-240 ℃, the hot air pressure is 0.1-0.3Mpa, the frequency of the main screw motor is 8-12Hz, the receiving distance is 20-30cm, and the rotating speed of the receiving roller is 75-85 m/min.
The invention also provides a nano silicon dioxide grafted halamine antibacterial melt-blown material which is prepared by the preparation method.
The invention also provides application of the nano silicon dioxide grafted halamine antibacterial melt-blown material, and the nano silicon dioxide grafted halamine antibacterial melt-blown material is used for preparing one or more antibacterial protective products in medical masks, medical protective clothing and industrial clothing.
The invention has the beneficial effects that:
(1) the preparation method of the nano-silica grafted halamine antibacterial melt-blown material provided by the invention utilizes the characteristics of hydrophilicity, high specific surface area and large amount of hydroxyl on the surface of hydrophilic nano-silica (compared with common nano-silica), provides more binding sites for a silane coupling agent, further provides more reaction sites for N-halamine, and uniformly bonds a large amount of mercaptosilane coupling agent on the surface of the hydrophilic nano-silica; then, the N-halamine precursor reacts with the sulfydryl of the silane coupling agent through a photoinitiator, so that the N-halamine precursor is uniformly bonded on the surface of the hydrophilic nano silicon dioxide; the addition of the hydrophilic silicon dioxide can also improve the mechanical property of the melt-blown material, and provides guarantee for the subsequent hypochlorous acid treatment, drying, hot pressing, electret treatment and repeated regeneration treatment of the melt-blown material; by utilizing the specific structure of the hydrophilic nano silicon dioxide and the three-dimensional disordered fiber structure of the polypropylene melt-blown material, the hydrophilic nano silicon dioxide is uniformly wrapped in the three-dimensional disordered fiber structure of the polypropylene melt-blown material, so that the antibacterial component is uniformly dispersed in the melt-blown material, and the obtained nano silicon dioxide grafted halamine antibacterial melt-blown material has higher antibacterial component content, is difficult to run off and has excellent antibacterial property. In addition, the hydrophilic nano silicon dioxide can store more charges when performing electret treatment, so that the electrostatic charge content in the melt-blown material is higher, and the service life of the filtering performance of the non-woven fabric is greatly prolonged; meanwhile, the interaction of the hydrophilic nano silicon dioxide with a special structure and the polypropylene melt-blown material with a three-dimensional disordered fiber structure can further improve the filtering effect, so that the finally prepared antibacterial melt-blown material has high antibacterial property and high filtering property; in addition, chlorination treatment is carried out firstly, and then electret treatment is carried out, so that the filtering performance of the melt-blown material is ensured to the maximum extent, and the melt-blown material is applied to the preparation of the protective mask.
(2) According to the preparation method of the nano silicon dioxide grafted halamine antibacterial melt-blown material, provided by the invention, the N-halamine precursor is bonded on the surface of the hydrophilic nano silicon dioxide by utilizing the photosensitivity of the mercaptosilane coupling agent and the photoinitiator, the mercapto group and the double bond react quickly under the ultraviolet light condition, so that the side reaction is avoided, the yield of the synthesized silicon dioxide grafted N-halamine precursor is high, and the finally prepared nano silicon dioxide grafted halamine antibacterial melt-blown material is high in antibacterial component content and good in antibacterial performance. Meanwhile, the photoinitiator has low toxicity and is less harmful to human bodies compared with a free radical initiator, and the photoinitiator only acts on the silicon dioxide grafted N-halamine process and is removed in a washing process, so that the harm to the subsequent process is avoided, and the safety coefficient of the material is improved.
(3) According to the preparation method of the nano silicon dioxide grafted halamine antibacterial melt-blown material, the N-halamine precursor is a double-bond-containing cyclic structure compound with a nitrogen atom ortho-position connected with an electron-withdrawing group, on one hand, the cyclic structure enables the stability of antibacterial components in the prepared melt-blown material to be high, and the failure and loss of the antibacterial components are avoided; on the other hand, when sterilization is carried out, the electron-withdrawing group connected with the ortho-position of the nitrogen atom limits the constraint effect of the nitrogen atom on the chlorine atom, so that the release efficiency of the active chlorine is greatly improved, the active chlorine is rapidly released, and the effect of rapid sterilization is achieved.
(4) The nano silicon dioxide grafted halamine antibacterial melt-blown material provided by the invention can realize the continuous conversion of N-Cl bonds and N-H bonds through simple treatment, so that the antibacterial effect of the melt-blown material is repeatedly regenerated. The antibacterial melt-blown material shows that the antibacterial effect on escherichia coli exceeds 99% in an antibacterial test, and the antibacterial effect on the escherichia coli still exceeds 98% after the escherichia coli is repeatedly regenerated through ten times of chlorination, so that conditions are provided for preparing antibacterial protective products such as medical protective clothing and industrial clothing. In addition, for the repeatedly regenerated melt-blown material, the filtering performance of the repeatedly regenerated melt-blown material can be improved again through secondary electret treatment, and repeated regeneration with high antibacterial efficiency and high filtering performance can be obtained.
Drawings
FIG. 1 is a graph showing the antibacterial effect of the nano-silica grafted halamine antibacterial meltblown material prepared in example 1 of the present invention on Escherichia coli.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a nano silicon dioxide grafted halamine antibacterial melt-blown material, which comprises the following steps:
s1, preparing modified silicon dioxide:
preparing isopropanol and water into a mixed solution according to the volume ratio of (2-5) to 1, and adding a gamma-mercaptopropyl trimethoxy silane coupling agent into the prepared mixed solution for hydrolysis to generate a silanol structure. Then adding hydrophilic nano silicon dioxide into the obtained solution, carrying out ultrasonic dispersion for 20-50min, and then heating and refluxing at 75-85 ℃. And finally, carrying out centrifugal washing on the mixed solution, and carrying out vacuum drying on a centrifugal product to obtain the modified silicon dioxide.
Wherein the mass ratio of the hydrophilic nano silicon dioxide to the gamma-mercaptopropyltrimethoxysilane coupling agent is (8-12) to (1-5).
In the process, hydrophilic silicon dioxide is adopted, and is uniformly dispersed in a mixed solution containing a gamma-mercaptopropyl trimethoxy silane coupling agent by utilizing the hydrophilicity of the hydrophilic silicon dioxide, and the agglomeration among nano silicon dioxide can be avoided; and then, by utilizing the unique pore structure and a large amount of hydroxyl (compared with common nano-silica), the silane coupling agent is quickly spread on the surface of the hydrophilic silica, and the silicon hydroxyl of the silanol structure in the hydrolyzed silane coupling agent molecule and the abundant hydroxyl on the surface of the hydrophilic silica form hydrogen bond action to further generate hydrolytic condensation reaction, so that the hydrophilic silica and the gamma-mercaptopropyl trimethoxy silane coupling agent form firm chemical bonds.
By utilizing the hydrophilicity, the unique pore structure and a large amount of hydroxyl of the hydrophilic silicon dioxide, a large amount of gamma-mercaptopropyl trimethoxy silane coupling agent is uniformly bonded on the surface of the silicon dioxide.
S2, preparation of silicon dioxide grafted N-halamine precursor powder:
and (2) uniformly mixing the modified nano-silica prepared in the step (S1), an N-halamine precursor and a photoinitiator, adding the mixture into a quartz bottle filled with absolute ethyl alcohol, placing the sealed quartz bottle on a magnetic stirring device for stirring, treating the quartz bottle with ultraviolet light for 2-4 hours, then carrying out centrifugal washing on the solution in the quartz bottle, removing the unreacted photoinitiator (improving the safety coefficient of the material), and carrying out vacuum drying to obtain the silicon dioxide grafted N-halamine precursor powder. Compared with liquid, the powdery substance has the advantages of small smell, small volatility and good safety.
Wherein the mass ratio of the modified nano silicon dioxide to the N-halamine precursor is (8-12) to (3-6); the mass of the photoinitiator accounts for 0.1-0.5% of the total mass of the modified nano silicon dioxide and the N-halamine precursor.
Specifically, the N-halamine precursor comprises one of methacrylamide, 1-allylhydantoin and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, and is preferably 1-allylhydantoin. The photoinitiator is benzoin dimethyl ether.
After the photoinitiator benzoin dimethyl ether absorbs energy through ultraviolet irradiation, the benzoin dimethyl ether is cracked into two oxygen radical active fragments, and the free radical fragments initiate photosensitive sulfydryl to be cracked into S-H bonds to form sulfydryl free radicals. The generated mercapto radical further generates polymerization reaction with allyl double bond in 1-allyl hydantoin, so that the gamma-mercaptopropyl trimethoxy silane coupling agent and the 1-allyl hydantoin form firm chemical bond.
Compared with a free radical grafting mode, the sulfydryl and the double bond have high reaction speed under the condition of ultraviolet light, can effectively avoid side reaction, has high reaction yield, and avoids the problem of material performance reduction caused by the addition of a free radical initiator by combining N-halamine and inorganic nano particles through photoinitiation.
Since a large amount of gamma-mercaptopropyltrimethoxysilane coupling agent is bonded to the surface of the modified silica prepared in the step S1, a large amount of 1-allylhydantoin can be bonded to the surface of the modified silica to form silica-grafted N-halamine precursor powder with uniform components and a large content of N-halamine precursor.
S3, preparing the silicon dioxide grafted N-halamine melt-blown material:
and (5) mixing the nano silicon dioxide grafted N-halamine precursor powder prepared in the step (S2) with melt-blown polypropylene resin according to the mass ratio of (2-5) to (80-100), and adding the mixture into a melt-blowing machine for melt-blowing treatment to obtain the silicon dioxide grafted N-halamine melt-blown material.
Wherein, the melt-blowing machine comprises four heating sections, the temperature setting range is 180-240 ℃, the hot air temperature is 220-240 ℃, the hot air pressure is 0.1-0.3Mpa, the frequency of the main screw motor is 8-12Hz, the receiving distance is 20-30cm, and the rotating speed of the receiving roller is 75-85 m/min.
The addition of the hydrophilic silicon dioxide can improve the mechanical property of the melt-blown material, and provides guarantee for the subsequent hypochlorous acid treatment, drying, hot pressing, electret treatment and repeated regeneration treatment of the melt-blown material.
S4, preparing the silicon dioxide grafted N-halamine antibacterial melt-blown material:
and (2) soaking the silicon dioxide grafted N-halamine melt-blown material prepared in the step (S3) in a prepared sodium hypochlorite solution with the pH value of 4-7 for 10-20min, wherein the pH value is preferably 5, N-H bonds in a halamine antibacterial agent are subjected to sodium hypochlorite action to generate N-Cl bonds capable of releasing active chlorine, taking out the melt-blown material and washing the melt-blown material to remove the residual sodium hypochlorite solution in the melt-blown material, and finally, drying, hot-pressing and electret treating the melt-blown material, wherein the electret voltage is 30-60KV, and the electret time is 1-2min, so that the nano silicon dioxide grafted N-halamine antibacterial melt-blown material is obtained.
The sodium hypochlorite solution is 20-30 times diluted by antipfurin, and 1 wt% of surfactant triton and dilute sulfuric acid are added into the sodium hypochlorite solution.
The electret melt-blown material has the advantages that the filtration efficiency is remarkably improved, and the melt-blown material with high antibacterial rate and high electret filtration property is obtained and can be applied to the preparation of protective masks.
For the repeatedly regenerated antibacterial melt-blown material, along with the soaking of the melt-blown material in a sodium hypochlorite solution, the filtering efficiency of the melt-blown material is reduced, mainly because the electrostatic charge of the electret melt-blown material can be lost into the solution in the soaking process of a chlorination solution, the electrostatic adsorption of the electrostatic charge is a core filtering mode of the melt-blown material on tiny germs, and the loss of the electrostatic charge can cause the reduction of the filtering effect. For medical protective clothing, industrial clothing and the like which mainly require repeated regeneration of antibacterial performance and do not require high filterability, the recycling of the melt-blown material can provide guarantee for the medical protective clothing, the industrial clothing and the like. If the filterability of the melt-blown material after the re-chlorination still has higher requirements, the filterability of the melt-blown material can be improved through electret treatment, so that the melt-blown material still keeps high antibacterial rate and electret filterability.
The invention also provides a nano silicon dioxide grafted halamine antibacterial melt-blown material which is prepared by the preparation method.
The invention also provides application of the nano silicon dioxide grafted halamine antibacterial melt-blown material, and the nano silicon dioxide grafted halamine antibacterial melt-blown material is used for preparing antibacterial protective products such as medical masks, medical protective clothing, industrial clothing and the like.
The invention is described in detail below by means of a number of examples:
example 1
A preparation method of a nano silicon dioxide grafted halamine antibacterial melt-blown material comprises the following steps:
s1, preparing modified silicon dioxide:
preparing isopropanol and water into a mixed solution according to the volume ratio of 3:1, and adding a gamma-mercaptopropyl trimethoxy silane coupling agent into the prepared mixed solution for hydrolysis to generate a silanol structure. Then adding hydrophilic nano silicon dioxide into the obtained solution, carrying out ultrasonic dispersion for 30min, and then heating and refluxing at 80 ℃. And finally, carrying out centrifugal washing on the mixed solution, and carrying out vacuum drying on a centrifugal product to obtain the modified silicon dioxide.
Wherein the mass ratio of the hydrophilic nano silicon dioxide to the gamma-mercaptopropyltrimethoxysilane coupling agent is 10: 3.
S2, preparation of silicon dioxide grafted N-halamine precursor powder:
and (4) uniformly mixing the modified nano-silica prepared in the step (S1), 1-allyl hydantoin and benzoin dimethyl ether, adding the mixture into a quartz bottle filled with absolute ethyl alcohol, placing the sealed quartz bottle on a magnetic stirring device for stirring, treating the quartz bottle with ultraviolet light for 3 hours, and then carrying out centrifugal washing and vacuum drying on the solution in the quartz bottle to obtain the precursor powder of the silicon dioxide grafted N-halamine.
Wherein the mass ratio of the modified nano silicon dioxide to the N-halamine precursor is 10: 4; the mass of the photoinitiator accounts for 0.3% of the total mass of the modified nano silicon dioxide and the N-halamine precursor.
S3, preparing the silicon dioxide grafted N-halamine melt-blown material:
and (4) mixing the nano silicon dioxide grafted N-halamine precursor powder prepared in the step (S2) with melt-blown polypropylene resin according to a preset ratio of 3:100, and adding the mixture into a melt-blowing machine for melt-blowing treatment to obtain the silicon dioxide grafted N-halamine melt-blown material.
Wherein, the melt-blowing machine comprises four heating sections, the temperature setting range is 180-240 ℃, the hot air temperature is 220-240 ℃, the hot air pressure is 0.21Mpa, the frequency of the main screw motor is 10Hz, the receiving distance is 24cm, and the rotating speed of the receiving roller is 80 m/min. The specific temperatures of the four heating sections were set as: 180 deg.C, 200 deg.C, 220 deg.C, 240 deg.C.
S4, preparing the silicon dioxide grafted N-halamine antibacterial melt-blown material:
and (2) soaking the silicon dioxide grafted N-halamine meltblown material prepared in the step (S3) in a prepared sodium hypochlorite solution with the pH value of 5 for 15min, allowing N-H bonds in a halamine antibacterial agent to act through sodium hypochlorite to generate N-Cl bonds capable of releasing active chlorine, taking out the meltblown material, washing the meltblown material to remove the sodium hypochlorite solution remained in the meltblown material, and finally drying, hot-pressing and electret treating the meltblown material at the electret voltage of 50KV for 2min to obtain the nano silicon dioxide grafted N-halamine antibacterial meltblown material.
The sodium hypochlorite solution is a solution diluted by 25 times by antipfurin, and 1 wt% of surfactant triton and dilute sulfuric acid are added into the sodium hypochlorite solution.
The prepared nano-silica grafted N-halamine antibacterial melt-blown non-woven fabric is subjected to escherichia coli antibacterial test (8099) (gram positive bacteria), fig. 1 shows that an oscillation method (oscillation 1h) is utilized to perform escherichia coli antibacterial performance test (two groups of parallel experiments are performed), a and b are control groups, c and d are experimental groups, and as can be seen from the figure, the nano-silica grafted N-halamine antibacterial melt-blown non-woven fabric prepared in the embodiment has good antibacterial performance, and the sterilization rate of escherichia coli reaches 99.9%.
Placing the nonwoven fabric subjected to the escherichia coli antibacterial test in a sodium thiosulfate aqueous solution, carrying out violent vortex for 1min and carrying out ultrasonic treatment for 5min, separating adhered bacteria from the surface of the nonwoven fabric into the solution, quenching the residual active chlorine, immersing the nonwoven fabric into a sodium hypochlorite solution again to generate active chlorine, and carrying out the escherichia coli antibacterial test, wherein the antibacterial effect of the nonwoven fabric on escherichia coli after ten chloridization reaches 98.9%.
The basic principle of the oscillation method test is as follows: the samples and the control components are respectively put into a triangular flask of test bacteria liquid with certain concentration, the triangular flask is oscillated for certain time at a specified temperature, the viable bacteria concentration of the bacteria liquid in the triangular flask before and after oscillation for certain time is measured, and the bacteriostasis rate is calculated, so that the antibacterial effect is evaluated.
Examples 2 to 3
Compared with the embodiment 1, the difference of the preparation method of the nano-silica grafted halamine antibacterial melt-blown material is that in the step S3, the mass ratio m of the nano-silica grafted N-halamine precursor powder to the melt-blown polypropylene resin is1:m2Otherwise, the rest is substantially the same as that of embodiment 1, and will not be described herein again.
The nano-silica grafted halamine antibacterial melt-blown materials prepared in examples 1-3 were subjected to performance tests, and the results are shown in table 1, wherein the bactericidal rate refers to the bactericidal rate of escherichia coli, and the filtration efficiency refers to the filtration efficiency of the melt-blown material (without repeated regeneration) after electret chlorination to 0.3 μm sodium chloride aerosol:
table 1 performance testing of nanosilica grafted halamine antibacterial meltblown materials prepared in examples 1-3
As can be seen from table 1, in example 2, the addition ratio of the nanosilicon dioxide grafted halamine powder is too low compared to example 1, which results in the decrease of the overall antibacterial performance and tensile strength of the meltblown material, and the decrease of the antibacterial performance is caused by the fact that only a small amount of antibacterial powder is exposed on the fiber surface of the meltblown material under the low content condition, so that the chlorinated meltblown material does not have the active chlorine content corresponding to the excellent antibacterial performance. In example 3, the nano silica grafted halamine powder is added in a large proportion, which causes the agglomeration among the powders to be increased, larger particles easily block spinneret holes, the spinneret process is discontinuous, and the fibers are not easy to form filaments, so that the finally prepared melt-blown material shows lower tensile strength.
Although the sterilization rate is reduced after ten times of chlorination, the reduction of the sterilization rate is little, which shows that the repeated sterilization and regeneration effect of the antibacterial melt-blown material is good. The melt-blown material can be recycled for medical protective clothing, industrial clothing and the like which do not mainly need high filterability.
The mass ratio of the nano silicon dioxide grafted N-halamine precursor powder to the melt-blown polypropylene resin is different, and the influence on the filtration efficiency of the melt-blown polypropylene material after primary chlorination and electret is small. Because the silicon dioxide can absorb static charge in the electret process and the filtering efficiency of the material can be further improved by adding the silicon dioxide into the melt-blown material, compared with the embodiment 1, the content of the nano silicon dioxide grafted N-halamine precursor in the embodiment 2 is low, and the filtering efficiency is slightly reduced; in example 3, the content of the added nano-silica grafted N-halamine precursor is high, and the filtration efficiency is slightly improved.
Examples 4 to 5
Compared with example 1, the difference of the preparation method of the nano-silica grafted halamine antibacterial melt-blown material is that in step S4, the pH value of the chlorination solution (sodium hypochlorite solution) is different from 5, and the rest is substantially the same as example 1, and will not be described herein again.
The nano-silica grafted halamine antibacterial melt-blown materials prepared in examples 4-5 were subjected to performance tests, and the results are shown in table 2, wherein the bactericidal rate refers to the bactericidal rate of escherichia coli, and the filtration efficiency refers to the filtration efficiency of the melt-blown material (without repeated regeneration) after electret chloride to 0.3 μm sodium chloride aerosol:
table 2 performance testing of nanosilica grafted halamine antibacterial meltblown materials prepared in examples 4-5
As can be seen from Table 2, the pH of the chlorination solution has a greater effect on the kill rate of the chlorinated meltblown material. This is because the reversible reaction of hypochlorite under acidic conditions tends to proceed more in the direction of the generation of more hypochlorous acid, where higher levels of hypochlorous acid will be more conducive to the conversion of N-H bonds to N-Cl bonds in the halamine precursor, resulting in higher active chlorine content in the chlorinated meltblown material. In example 4, the chlorinated meltblown material had a certain active chlorine content in a neutral environment, but the antimicrobial properties were not sufficient compared to example 1 in an acidic environment. In example 5, the hypochlorous acid content in the alkaline environment was very low, which indirectly resulted in very low conversion efficiency of the haloamine precursor N-H bond to N-Cl bond, and therefore the chlorinated melt-blown material had very low active chlorine content and very poor bactericidal effect.
When the chlorination solution is in an acidic condition, the reduction of the sterilization rate after ten times of chlorination is little; and when the chlorination solution is in a neutral or alkaline condition, the reduction of the sterilization rate after ten times of chlorination is faster, which further indicates that the method is beneficial to the conversion of N-H bonds in the halamine precursor to N-Cl bonds under an acidic condition.
The pH value of the chlorination solution has no influence on the filtration efficiency of the melt-blown material after the melt-blown material is firstly chlorinated and electret.
Examples 6 to 7
Compared with the embodiment 1, the difference of the preparation method of the nano-silica grafted halamine antibacterial melt-blown material is that in the step S4, the soaking time of the melt-blown material in the chlorination solution is different, and the rest is substantially the same as that of the embodiment 1, and the details are not repeated herein.
The nano-silica grafted halamine antibacterial melt-blown materials prepared in examples 6-7 were subjected to performance tests, and the results are shown in table 3, wherein the bactericidal rate refers to the bactericidal rate of escherichia coli, the filtration efficiency refers to the filtration efficiency of the melt-blown material (without repeated regeneration) after chlorination of the electret to 0.3 μm sodium chloride aerosol, and the regeneration filtration efficiency refers to the filtration efficiency after ten chlorination regeneration of the melt-blown material without electret:
table 3 performance testing of nanosilica grafted halamine antibacterial meltblown materials prepared in examples 6-7
As can be seen from table 3, the sterilizing rate of the meltblown material increased with the soaking time. In example 6, the immersion time of the meltblown material in the chlorinated solution was shorter than that in example 1, and the time required for the conversion of the N — H bond to the N — Cl bond of the halamine precursor was insufficient, so that the content of active chlorine was lower than that in example 1, and the sterilization rate was inferior to that in example 1. In example 7, the soaking time was sufficient, and the conversion rate of the N-H bond to the N-Cl bond in the halamine precursor was higher, so that the sterilization rate tended to be slightly higher than that in example 1.
The different soaking time of the melt-blown material in the chlorination solution has no influence on the filtration efficiency of the melt-blown material after the melt-blown material is firstly chlorinated and electret.
With the re-soaking of the melt-blown material in the sodium hypochlorite solution, the filtration efficiency of the regenerated melt-blown material is reduced, but the filtration efficiency is still higher, and the regenerated melt-blown material can be used as the melt-blown material with high antibacterial efficiency and certain regeneration filtration efficiency for protective clothing and the like which do not mainly need regeneration filtration performance. In addition, the melt-blown material regenerated by multiple chloridization can improve the regeneration filterability through electret treatment, and the melt-blown material with high antibacterial efficiency and high electret filterability can be obtained, so that the melt-blown material can be recycled.
Comparative example 1
Compared with the embodiment 1, the difference of the preparation method of the nano-silica grafted halamine antibacterial melt-blown material is that in the step S2, the N-halamine precursor is methacrylamide with a chain structure, and the N ortho position is not connected with an electron-withdrawing group, and the rest is substantially the same as the embodiment 1, and is not repeated herein.
The antibacterial rate of the obtained antibacterial melt-blown material to escherichia coli is 85.1%, and the sterilization rate after ten-time chlorination is 70.3%, so that the N-halamine precursor with the N-ortho-position connected with the electron-withdrawing group and the double-bond cyclic structure can improve the sterilization rate of the melt-blown material.
In conclusion, the nano silicon dioxide grafted halamine antibacterial melt-blown material and the preparation method and application thereof provided by the invention have the advantages that silicon dioxide and an N-halamine precursor are connected by using a silane coupling agent and added into a melt-blown polypropylene non-woven fabric, so that the non-woven fabric is endowed with a high-efficiency sterilization and antiviral effect, the antibacterial effect can be repeatedly regenerated through simple treatment, the electrostatic charge content in the non-woven fabric after electret is further improved by adding the silicon dioxide, the filtering performance of the non-woven fabric is improved, and the service life of the non-woven fabric is greatly prolonged. Compared with a free radical grafting mode, the N-halamine and the inorganic nanoparticles are combined, the problem of performance reduction of the material caused by the addition of an initiator is further solved, the high specific area of the inorganic nanoparticles provides more reaction sites for the N-halamine, and the N-halamine and the polymer material are blended and dispersed to give the material an integral antibacterial function to a greater extent.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a nano silicon dioxide grafted halamine antibacterial melt-blown material is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing modified silicon dioxide: adding hydrophilic nano-silica into a mercaptosilane coupling agent solution prepared from isopropanol and water according to a preset proportion, and performing ultrasonic dispersion, heating reflux, centrifugal washing and drying to obtain modified silica;
s2, preparation of silicon dioxide grafted N-halamine precursor powder: uniformly mixing the modified nano-silica prepared in the step S1 with an N-halamine precursor and a photoinitiator, adding the mixture into absolute ethyl alcohol, treating the mixture for 2 to 4 hours by using ultraviolet light, and performing centrifugal washing and vacuum drying to obtain silicon dioxide grafted N-halamine precursor powder;
s3, preparing the silicon dioxide grafted N-halamine melt-blown material: mixing the nano silicon dioxide grafted N-halamine precursor powder prepared in the step S2 with melt-blown polypropylene resin according to a preset proportion, and adding the mixture into a melt-blown machine for melt-blowing treatment to obtain a silicon dioxide grafted N-halamine melt-blown material;
s4, preparing the silicon dioxide grafted N-halamine antibacterial melt-blown material: and (4) soaking the silicon dioxide grafted N-halamine melt-blown material prepared in the step (S3) in a sodium hypochlorite solution for 10-20min, and performing washing, drying, hot pressing and electret treatment to obtain the nano silicon dioxide grafted N-halamine antibacterial melt-blown material.
2. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 1, wherein the method comprises the following steps: in the step S3, the mass ratio of the nano silicon dioxide grafted N-halamine precursor powder to the melt-blown polypropylene resin is (2-5): (80-100).
3. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 1, wherein the method comprises the following steps: in the step S4, the sodium hypochlorite solution is a solution diluted by 20-30 times by antipfurin, 1 wt% of a surfactant and a pH regulator are added into the sodium hypochlorite solution, and the pH value of the sodium hypochlorite solution is 4-7.
4. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 3, wherein: the surface ionic active agent is triton; the pH regulator is dilute sulfuric acid.
5. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 1, wherein the method comprises the following steps: in the step S1, the mass ratio of the nano silicon dioxide to the mercaptosilane coupling agent is (8-12): 1-5, and the volume ratio of the isopropanol to the water is (2-5): 1.
6. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 1, wherein the method comprises the following steps: the N-halamine precursor in step S2 includes one of methacrylamide, 1-allylhydantoin, and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine.
7. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 1, wherein the method comprises the following steps: in the step S2, the mass ratio of the modified nano silicon dioxide to the N-halamine precursor is (8-12) to (3-6); the mass of the photoinitiator accounts for 0.1-0.5% of the total mass of the modified nano silicon dioxide and the N-halamine precursor; the photoinitiator is benzoin dimethyl ether.
8. The method for preparing nano-silica grafted halamine antibacterial melt-blown material according to claim 1, wherein the method comprises the following steps: in step S3, the melt blowing machine comprises four heating sections, the temperature setting range is 180-240 ℃, the hot air temperature is 220-240 ℃, the hot air pressure is 0.1-0.3Mpa, the frequency of the main screw motor is 8-12Hz, the receiving distance is 20-30cm, and the rotating speed of the receiving roller is 75-85 m/min.
9. A nano silicon dioxide grafted halamine antibacterial melt-blown material is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. Use of a nanosilica-grafted halamine antibacterial meltblown material prepared by the method of preparation according to any of claims 1 to 8 or of a nanosilica-grafted halamine antibacterial meltblown material according to claim 9, characterized in that: the nano silicon dioxide grafted halamine antibacterial melt-blown material is used for preparing one or more antibacterial protective products in medical masks, medical protective clothing and industrial clothing.
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