CN114395861B - 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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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- 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
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- 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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- 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
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- 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
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- 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
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Abstract
The invention provides a nano silicon dioxide grafted halamine antibacterial melt-blown material, a preparation method and application thereof. The preparation method comprises the following steps: adding hydrophilic nano silicon dioxide into a mercapto silane coupling agent solution, and reacting to obtain modified silicon dioxide; bonding the modified nano silicon dioxide with an N-halamine precursor by utilizing 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 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 time, long service life and repeatedly regenerated antibacterial components.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a silica grafted halamine antibacterial melt-blown material and a preparation method and application thereof.
Background
In the global context of influenza pandemic, medical masks are becoming an necessity for people's daily life. As a core material of the medical mask, the polypropylene melt-blown material utilizes a three-dimensional disordered fiber structure to adsorb and block invasion of external pathogens. However, because polypropylene has no bactericidal and antiviral effects, pathogens blocked on the mask still survive, and if the mask is improperly operated in the process of wearing, the risk of infection to human bodies is extremely easy to cause; and the used mask can generate potential infection sources if not properly treated in time, thereby threatening the life safety of other people. In recent five years, the production value of masks in China is increased year by year, the proportion of medical masks is increased year by year, and the core material of the main flow masks in the current market is still an 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, and has a fast sterilization rate and a stable and long-lasting effect, wherein the active chlorine component playing an antibacterial role can be repeatedly regenerated through the chlorination treatment of sodium hypochlorite solution. At present, the preparation of antibacterial materials by grafting N-halamine precursors containing double bonds onto polymer molecular chains using free radical initiators has been studied extensively. However, the addition of the 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 the polymerization of the functional monomer itself, which not only affects the processability of the polymer but also makes the functional monomer useless, and the radical initiator may remain in the polymer material eventually, which may cause potential safety problems if the polymer material is in direct contact with the human body.
Patent application number CN202010711332.6 discloses an antibacterial polypropylene melt-blown material, a preparation method and application thereof, wherein polypropylene is used as a matrix material, 1-vinylimidazole is used as an antibacterial monomer, the antibacterial monomer is grafted onto a main chain of polypropylene to form a polypropylene melt-blown material intermediate, and then amine halogenation is carried out to obtain the antibacterial polypropylene melt-blown material. The method has the following defects: the introduced 1-vinyl imidazole makes the smell of the material extremely large, and potential safety hazards exist; and halogen element in nitrogen-halogen bond in common vinyl imidazole five-membered ring is not easy to release, so that the antibacterial effect is poor.
In view of the foregoing, there is a need for an improved silica grafted haloamine antimicrobial meltblown material, and methods of making and using the same, which address the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a silica grafted halamine antibacterial melt-blown material, a preparation method and application thereof, wherein N-halamine precursors with a double bond-containing annular structure, which are connected with electron withdrawing groups at N ortho positions, are uniformly bonded to the surface of hydrophilic silica, and then are blended with a polypropylene melt-blown material for melt-blowing, chlorination and electret treatment, so that the melt-blown material with high antibacterial property and high electret filtering property is obtained, and the antibacterial effect can be repeatedly regenerated.
In order to achieve the aim of the invention, 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 silicon dioxide into a sulfhydryl silane coupling agent solution prepared by isopropanol and water according to a preset proportion, and carrying out ultrasonic dispersion, heating reflux, centrifugal washing and drying to obtain modified silicon dioxide;
s2, preparing silicon dioxide grafted N-halamine precursor powder: uniformly mixing the modified nano silicon dioxide prepared in the step S1, an N-halamine precursor and a photoinitiator, adding the mixture into absolute ethyl alcohol, treating the mixture for 2 to 4 hours by ultraviolet light, and obtaining silicon dioxide grafted N-halamine precursor powder through centrifugal washing and vacuum drying;
s3, preparing a 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-blowing machine for melt-blowing treatment to obtain a silicon dioxide grafted N-halamine melt-blown material;
s4, preparing a silicon dioxide grafted N-halamine antibacterial melt-blown material: and (3) 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 silicon dioxide grafted N-halamine precursor powder to the melt-blown polypropylene resin in the step S3 is (2-5): 80-100.
As a further improvement of the invention, the sodium hypochlorite solution in the step S4 is a 20-30 times diluted solution of An Tifu min, and 1wt% of a surfactant and a pH regulator are added into the sodium hypochlorite solution, wherein the pH value 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 silicon dioxide to the mercapto silane coupling agent in the step S1 is (8-12): (1-5), and the volume ratio of the isopropyl alcohol to the water is (2-5): 1.
As a further improvement of the present invention, the N-halamine precursor in step S2 comprises one of methacrylamide, 1-allyl hydantoin, 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): 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, the melt-blowing machine in the step S3 comprises four heating sections, the temperature setting range is 180-240 ℃, the hot air flow temperature is 220-240 ℃, the hot air flow pressure is 0.1-0.3Mpa, the frequency of a main screw motor is 8-12Hz, the receiving distance is 20-30cm, and the rotating speed of a receiving roller is 75-85m/min.
The invention also provides a nano silicon dioxide grafted halamine antibacterial melt-blown material, which is prepared by adopting the preparation method.
The invention also provides application of the nano-silica grafted halamine antibacterial melt-blown material, which is used for preparing one or more antibacterial protective products in medical masks, medical protective clothing and industrial clothing.
The beneficial effects of the invention are as follows:
(1) According to the preparation method of the nano silicon dioxide grafted halamine antibacterial melt-blown material, provided by the invention, by utilizing the characteristics of hydrophilicity, high specific surface area and large number of hydroxyl groups on the surface of the hydrophilic nano silicon dioxide (compared with common nano silicon dioxide), more binding sites are provided for a silane coupling agent, more reaction sites are provided for N-halamine, and a large number of sulfhydryl silane coupling agents are uniformly bonded on the surface of the hydrophilic nano silicon dioxide; then the N-halamine precursor reacts with sulfhydryl of the silane coupling agent through the 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 provide guarantee for the subsequent hypochlorous acid treatment, drying, hot pressing, electret treatment and repeated regeneration treatment of the melt-blown material; the hydrophilic nano silicon dioxide is uniformly wrapped in the three-dimensional disordered fiber structure of the polypropylene melt-blown material by utilizing the special structure of the hydrophilic nano silicon dioxide and the three-dimensional disordered fiber structure of the polypropylene melt-blown material, so that antibacterial components are 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 not easy to run off and has excellent antibacterial property. In addition, the hydrophilic nano silicon dioxide can store more charges when subjected to electret treatment, so that the static 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 between 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, the invention carries out chlorination treatment and then electret treatment, so that the filtering performance of the melt-blown material is ensured to the greatest extent, and the melt-blown material is applied to the preparation of protective masks.
(2) According to the preparation method of the nano silicon dioxide grafted halamine antibacterial melt-blown material, provided by the invention, the photosensitivity of the sulfhydryl silane coupling agent is utilized, the N-halamine precursor is bonded to the surface of the hydrophilic nano silicon dioxide through the photoinitiator, the sulfhydryl and double bonds react rapidly under the ultraviolet light condition, the occurrence of 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 has high antibacterial component content and good antibacterial property. Meanwhile, the photoinitiator has low toxicity, compared with a free radical initiator, has low harm to human bodies, and only acts on the silicon dioxide grafted N-halamine in the process of removing the photoinitiator through a washing process, so that the damage 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 compound with a double bond and a ring structure, wherein the compound is connected with an electron withdrawing group at the ortho position of a nitrogen atom, so that on one hand, the stability of antibacterial components in the prepared melt-blown material is higher due to the ring structure, 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 action of the nitrogen atom on the chlorine atom, so that the release efficiency of the active chlorine is greatly improved, the rapid release of the active chlorine is realized, and the rapid sterilization effect is achieved.
(4) The nano silicon dioxide grafted halamine antibacterial melt-blown material provided by the invention can realize continuous conversion of N-Cl bond and N-H bond 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 the escherichia coli exceeds 99 percent in an antibacterial test, and the antibacterial effect on the escherichia coli still exceeds 98 percent after repeated chlorination regeneration for ten times, thereby providing conditions for preparing antibacterial protective products such as medical protective clothing, industrial clothing and the like. In addition, the filter performance of the repeatedly regenerated melt-blown material can be improved again through secondary electret treatment, and the repeatedly regenerated melt-blown material with high antibacterial efficiency and high filter performance can be obtained.
Drawings
FIG. 1 is a graph showing the antibacterial effect of the nano-silica grafted haloamine antibacterial meltblown material prepared in example 1 of the present invention on E.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 due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further 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:
mixing isopropanol and water in the volume ratio of (2-5) to 1 to obtain mixed solution, and adding gamma-mercaptopropyl trimethoxy silane coupling agent into the mixed solution to hydrolyze to obtain 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, centrifugally washing the mixed solution, and vacuum drying the centrifugal product to obtain the modified silicon dioxide.
Wherein the mass ratio of the hydrophilic nano silicon dioxide to the gamma-mercaptopropyl trimethoxy silane coupling agent is (8-12) to (1-5).
The hydrophilic silicon dioxide is adopted in the process, and the hydrophilic silicon dioxide is utilized to uniformly disperse the hydrophilic silicon dioxide in the mixed solution containing the gamma-mercaptopropyl trimethoxy silane coupling agent, so that agglomeration among nano silicon dioxide can be avoided; and then the unique pore structure and a large number of hydroxyl groups (compared with common nano silicon dioxide) of the hydrophilic silicon dioxide are utilized, the silane coupling agent is rapidly spread on the surface of the hydrophilic silicon dioxide, and the silanol-structured silicon hydroxyl groups in the hydrolyzed silane coupling agent molecules and the hydroxyl groups on the surface of the hydrophilic silicon dioxide form hydrogen bond action, so that hydrolysis condensation reaction occurs, and the hydrophilic silicon dioxide and the gamma-mercaptopropyl trimethoxy silane coupling agent form firm chemical bonds.
The hydrophilicity, unique pore structure and great amount of hydroxyl groups of hydrophilic silica are utilized to make great amount of gamma-mercaptopropyl trimethoxy silane as coupling agent bond homogeneously to the surface of silica.
S2, preparing silicon dioxide grafted N-halamine precursor powder:
uniformly mixing the modified nano silicon dioxide 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, centrifuging and washing a solution in the quartz bottle to remove unreacted photoinitiator (improve the safety coefficient of the material), and vacuum drying to obtain silicon dioxide grafted N-halamine precursor powder. Compared with liquid, the powder material has small smell, low volatility and good safety.
Wherein the mass ratio of the modified nano silicon dioxide to the N-halamine precursor is (8-12) (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-allyl hydantoin and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, and preferably 1-allyl hydantoin. The photoinitiator is benzoin dimethyl ether.
After the photoinitiator benzoin dimethyl ether absorbs energy through ultraviolet irradiation, benzoin dimethyl ether is cracked into two oxygen free radical active fragments, and the free radical fragments trigger photosensitive sulfhydryl groups to generate S-H bond cleavage, so that sulfhydryl free radicals are formed. The generated sulfhydryl free radical further carries out polymerization reaction with allyl double bond in the 1-allyl hydantoin, so that the gamma-mercaptopropyl trimethoxy silane coupling agent and the 1-allyl hydantoin form firm chemical bond.
Compared with the free radical grafting mode, the method has the advantages that the reaction speed of the sulfhydryl group and the double bond is high under the ultraviolet light condition, the occurrence of side reaction can be effectively avoided, the reaction yield is high, and the problem of material performance reduction caused by the addition of the free radical initiator is avoided by combining the N-halamine with the inorganic nano particles through photoinitiation.
Because a large amount of gamma-mercaptopropyl trimethoxy silane coupling agent is bonded on the surface of the modified silicon dioxide prepared in the step S1, a large amount of 1-allyl hydantoin is bonded on the surface of the modified silicon dioxide, and silicon dioxide grafted N-halamine precursor powder with uniform components and high N-halamine precursor content is formed.
S3, preparing a silicon dioxide grafted N-halamine melt-blown material:
and (3) 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) (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 large heating sections, the temperature setting range is 180-240 ℃, the hot air flow temperature is 220-240 ℃, the hot air flow pressure is 0.1-0.3Mpa, the frequency of a main screw motor is 8-12Hz, the receiving distance is 20-30cm, and the rotating speed of a receiving roller is 75-85m/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 a silicon dioxide grafted N-halamine antibacterial melt-blown material:
and (3) immersing the silica 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 the halamine antibacterial agent are subjected to the action of sodium hypochlorite to generate N-Cl bonds capable of releasing active chlorine, taking out the melt-blown material, flushing the melt-blown material to remove the sodium hypochlorite solution remained in the melt-blown material, and finally drying, hot-pressing and carrying out electret treatment on the melt-blown material, wherein the electret voltage is 30-60KV, and the electret time is 1-2min, so that the nano silica grafted N-halamine antibacterial melt-blown material is obtained.
The sodium hypochlorite solution is a 20-30 times diluted solution of An Tifu people, and 1wt% of surfactant triton and dilute sulfuric acid are added into the sodium hypochlorite solution.
The filtering efficiency of the melt-blown material after electret is obviously improved, and the melt-blown material with high antibacterial rate and high electret filterability is obtained, and can be applied to the preparation of protective masks.
For the repeatedly regenerated antibacterial melt-blown material, the filtration efficiency of the melt-blown material is reduced along with the soaking of the melt-blown material in a sodium hypochlorite solution, mainly because the static charge of the electret melt-blown material is lost into the solution in the chloridizing solution soaking process, and the static adsorption of the static charge is a core filtration mode of the melt-blown material to tiny germs, and the loss of the static charge leads to the reduction of the filtration effect. For medical protective clothing, industrial clothing and the like which take the repeated regeneration of antibacterial performance as main requirements and do not take higher filterability as main requirements, the recycling of the melt-blown material can provide guarantee for the melt-blown material. 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 by electret treatment, so that the melt-blown material still has high antibacterial rate and high electret filterability.
The invention also provides a nano silicon dioxide grafted halamine antibacterial melt-blown material, which is prepared by adopting the preparation method.
The invention also provides application of the nano-silica grafted halamine antibacterial melt-blown material, and the nano-silica grafted halamine antibacterial melt-blown material is used for preparing antibacterial protection products such as medical masks, medical protective clothing, industrial clothing and the like.
The invention is described in detail below by means of several examples:
example 1
The preparation process of nanometer silica grafted haloamine antibacterial melt blown material includes the following steps:
s1, preparing modified silicon dioxide:
preparing a mixed solution from isopropanol and water according to a 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, centrifugally washing the mixed solution, and vacuum drying the centrifugal product to obtain the modified silicon dioxide.
Wherein the mass ratio of the hydrophilic nano silicon dioxide to the gamma-mercaptopropyl trimethoxy silane coupling agent is 10:3.
S2, preparing silicon dioxide grafted N-halamine precursor powder:
uniformly mixing the modified nano silicon dioxide 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 centrifugally washing and vacuum drying the solution in the quartz bottle to obtain the silicon dioxide grafted N-halamine precursor powder.
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 a silicon dioxide grafted N-halamine melt-blown material:
and (2) 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 large heating sections, the temperature setting range is 180-240 ℃, the hot air flow temperature is 220-240 ℃, the hot air flow pressure is 0.21Mpa, the frequency of a main screw motor is 10Hz, the receiving distance is 24cm, and the rotating speed of a receiving roller is 80m/min. The specific temperature of the four heating sections is set as follows: 180 ℃, 200 ℃, 220 ℃, 240 ℃.
S4, preparing a silicon dioxide grafted N-halamine antibacterial melt-blown material:
and (3) 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 5 for 15min, generating N-Cl bond capable of releasing active chlorine after the N-H bond in halamine antibacterial agent is acted by sodium hypochlorite, taking out the melt-blown material, flushing the melt-blown material to remove the sodium hypochlorite solution remained in the melt-blown material, and finally drying, hot-pressing and carrying out residence treatment on the melt-blown material, wherein the residence voltage is 50KV, and the residence time is 2min, so that the nano silicon dioxide grafted N-halamine antibacterial melt-blown material is obtained.
The sodium hypochlorite solution is a solution diluted by An Tifu times, and 1wt% of surfactant triton and dilute sulfuric acid are added into the sodium hypochlorite solution.
The prepared nano silicon dioxide grafted N-halamine antibacterial melt-blown non-woven fabric is subjected to an escherichia coli antibacterial test (8099) (gram positive bacteria), and fig. 1 shows that the escherichia coli antibacterial performance test (two groups of parallel experiments are carried out) is carried out by using an oscillation method (oscillation for 1 h), a and b are control groups, c and d are experimental groups, and the nano silicon dioxide grafted N-halamine antibacterial melt-blown non-woven fabric prepared by the embodiment has good antibacterial performance, and the sterilization rate of the escherichia coli reaches 99.9%.
Placing the non-woven fabric subjected to the escherichia coli antibacterial test in a sodium thiosulfate aqueous solution, carrying out intense vortex for 1min and ultrasonic treatment for 5min, separating adhered bacteria from the surface of the non-woven fabric into the solution, quenching residual active chlorine, immersing the non-woven 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 non-woven fabric on the escherichia coli reaches 98.9% after ten times of chlorination.
The basic principle of the oscillation method test is as follows: the antibacterial effect is evaluated by respectively filling the sample and the control into an Erlenmeyer flask with a test bacterial liquid of a certain concentration, shaking for a certain time at a specified temperature, measuring the viable bacterial concentration of the bacterial liquid in the Erlenmeyer flask before and after shaking for a certain time, and calculating the antibacterial rate.
Examples 2 to 3
The preparation method of nano silicon dioxide grafted halamine antibacterial melt-blown material is different from example 1 in that in step S3, the mass ratio m of nano silicon dioxide grafted N-halamine precursor powder to melt-blown polypropylene resin 1 :m 2 Other differences are substantially the same as those of embodiment 1, and will not be described here again.
The performance of the nano silica grafted halamine antibacterial meltblown materials prepared in examples 1-3 is tested, and the results are shown in table 1, wherein the sterilization rate refers to the sterilization rate of escherichia coli, and the filtration efficiency refers to the filtration efficiency of the meltblown material (without repeated regeneration) after chlorination and residence to 0.3 μm sodium chloride aerosol:
TABLE 1 Performance test of nanosilica grafted haloamine antibacterial meltblown materials prepared in examples 1-3
As can be seen from table 1, compared with example 1, the addition ratio of the nano silica grafted halamine powder in example 2 is too small, 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 due to the fact that only a small amount of antibacterial powder is exposed on the fiber surface of the meltblown material under the condition of low content, so that the chlorinated meltblown material does not have the active chlorine content corresponding to the excellent antibacterial performance. In example 3, excessive addition ratio of nano silica grafted halamine powder can cause agglomeration and weight increase among the powder, larger particles are easy to block spinneret orifices, the spinneret process is discontinuous, and 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 small, which proves that the repeated sterilization and regeneration effects of the antibacterial melt-blown material are good. For medical protective clothing, industrial clothing and the like which do not have higher filterability as main requirements, the melt-blown material can be recycled.
The mass ratio of the nano silicon dioxide grafted N-halamine precursor powder to the melt-blown polypropylene resin is different, so that the filtration efficiency of the melt-blown polypropylene material after the first chlorination and residence is less affected. Because the silicon dioxide can adsorb static charges in the electret process, 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 nano silicon dioxide grafted N-halamine precursor in the embodiment 2 has low addition content, and the filtering efficiency is slightly reduced; in the embodiment 3, the nano silicon dioxide grafted N-halamine precursor has high addition content, and the filtration efficiency is slightly improved.
Examples 4 to 5
The preparation method of the nano-silica grafted halamine antibacterial melt-blown material is different from that of the embodiment 1 in that in the step S4, the pH 5 of the chlorinated solution (sodium hypochlorite solution) is different, and the other steps are substantially the same as those of the embodiment 1, and are not described herein.
The performance of the nano silica grafted halamine antibacterial meltblown materials prepared in examples 4-5 is tested, and the results are shown in table 2, wherein the sterilization rate refers to the sterilization rate of escherichia coli, and the filtration efficiency refers to the filtration efficiency of the meltblown material after chlorination and residence (without repeated regeneration) on 0.3 μm sodium chloride aerosol:
TABLE 2 Performance test of nanosilica grafted haloamine antibacterial meltblown materials prepared in examples 4-5
As can be seen from Table 2, the pH of the chlorinated solution has a large effect on the sterilization rate of the chlorinated melt blown material. This is because under acidic conditions, the reversible reaction of hypochlorite is more prone to proceed in the direction of more hypochlorous acid generation, where higher levels of hypochlorous acid would be more beneficial for the conversion of N-H bonds to N-Cl bonds in the haloamine precursor, resulting in higher levels of active chlorine in the chlorinated meltblown material. In example 4, the chlorinated melt blown material had a certain active chlorine content in a neutral environment, but there was still a certain difference in antimicrobial properties compared to example 1 in an acidic environment. In example 5, the hypochlorous acid content in the alkaline environment is extremely low, which indirectly leads to extremely low conversion efficiency of N-H bond of the halamine precursor into N-Cl bond, so that the active chlorine content in the chlorinated melt blown material is extremely low, and the sterilization effect is extremely poor.
When the chloridizing solution is in an acidic condition, the sterilization rate is reduced slightly after ten times of chloridization; and when the chloridizing solution is in a neutral or alkaline condition, the sterilization rate is reduced rapidly after ten times of chloridization, which further proves that the conversion of N-H bond in the haloamine precursor to N-Cl bond is beneficial under an acidic condition.
The pH value of the chloridizing solution has no influence on the filtration efficiency of the melt-blown material after the first chlorination and residence.
Examples 6 to 7
The preparation method of the nano silica grafted halamine antibacterial melt-blown material is different from that of the embodiment 1 in that in the step S4, the soaking time of the melt-blown material in the chloridized solution is different, and the other steps are substantially the same as those of the embodiment 1, and are not repeated here.
The performance test is carried out on the nano silica grafted halamine antibacterial melt-blown material prepared in examples 6-7, the result is shown in table 3, the sterilization rate refers to the sterilization rate of escherichia coli, the filtration efficiency refers to the filtration efficiency of the melt-blown material after chlorination and electret (without repeated regeneration) to 0.3 mu m sodium chloride aerosol, and the regeneration filtration efficiency refers to the filtration efficiency of the melt-blown material after ten chlorination regenerations without electret:
TABLE 3 Performance test of nanosilica grafted haloamine antibacterial meltblown materials prepared in examples 6-7
As can be seen from Table 3, the sterilization rate of the meltblown material increased with longer soaking time. In example 6, the soaking time of the meltblown material in the chlorinated solution was shorter than in example 1, and the conversion of the N-H bond of the haloamine precursor to the N-Cl bond required was insufficient, and thus the sterilizing rate was lower in active chlorine content than in example 1, and was inferior to that of example 1. In example 7, the conversion rate of N-H bond to N-Cl bond of the halamine precursor was higher due to the sufficient soaking time, so that the sterilization rate had a slightly increased tendency compared with example 1.
The different soaking time of the melt-blown material in the chloridizing solution has no influence on the filtering efficiency of the melt-blown material after the first chlorination and the residence.
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 relatively high, and the regenerated melt-blown material can be used as the melt-blown material with high antibacterial efficiency and certain regeneration filtration efficiency again for protective clothing and the like which do not take the regeneration filtration performance as main requirements. In addition, the regenerated melt-blown material after multiple chlorination can also be subjected to electret treatment to improve the regeneration filterability, so that the melt-blown material with high antibacterial efficiency and high electret filterability can be obtained, and the melt-blown material can be recycled.
Comparative example 1
Compared with the embodiment 1, the preparation method of the nano silica grafted halamine antibacterial melt-blown material is different in 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 other positions are approximately the same as the embodiment 1, and are not repeated.
The antibacterial rate of the obtained antibacterial melt-blown material on escherichia coli is 85.1 percent, and the sterilization rate after ten times of chlorination is 70.3 percent, so that the N-halamine precursor with the N ortho-position connected with the electron withdrawing group and containing the double bond and having a ring structure can be further explained, and the sterilization rate of the melt-blown material can be improved.
In summary, according to the nano silicon dioxide grafted halamine antibacterial melt-blown material, the preparation method and the application thereof, the silicon dioxide and the N-halamine precursor are connected by using the silane coupling agent and added into the melt-blown polypropylene non-woven fabric, so that the non-woven fabric is endowed with high-efficiency sterilization and antiviral effects, the repeated regeneration of the antibacterial effects can be realized through simple treatment, the static charge content in the non-woven fabric after residence is further improved by adding the silicon dioxide, the filtering performance is improved, and the service life of the non-woven fabric is greatly prolonged. Compared with a free radical grafting mode, the N-halamine is combined with the inorganic nano particles, the problem of material performance reduction caused by the addition of an initiator is further solved, the high specific area of the inorganic nano particles provides more reaction sites for the N-halamine, and the material is endowed with an overall antibacterial function to a greater extent after being blended and dispersed with a polymer material.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of nano silicon dioxide grafted halamine antibacterial melt-blown material is characterized by comprising the following steps of: the method comprises the following steps:
s1, preparing modified nano silicon dioxide: 1, preparing mixed solution by isopropanol and water according to the volume ratio of (2-5), and adding a mercapto silane coupling agent into the mixed solution for hydrolysis; adding hydrophilic nano silicon dioxide, performing ultrasonic dispersion for 20-50min, heating and refluxing at 75-85 ℃, and performing centrifugal washing and drying to obtain modified nano silicon dioxide; the mass ratio of the hydrophilic nano silicon dioxide to the mercapto silane coupling agent is (8-12): 1-5;
s2, preparing nano silicon dioxide grafted N-halamine precursor powder: uniformly mixing the modified nano silicon dioxide prepared in the step S1, an N-halamine precursor and a photoinitiator, adding the mixture into absolute ethyl alcohol, treating the mixture for 2 to 4 hours by ultraviolet light, and obtaining nano silicon dioxide grafted N-halamine precursor powder through centrifugal washing and vacuum drying; the N-halamine precursor is 1-allyl hydantoin; the photoinitiator is benzoin dimethyl ether;
s3, preparing a nano 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-blowing machine for melt-blowing treatment to obtain a nano silicon dioxide grafted N-halamine melt-blown material;
s4, preparing a nano silicon dioxide grafted N-halamine antibacterial melt-blown material: soaking the nano 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; the sodium hypochlorite solution is a 20-30 times diluted solution of An Tifu people, and is added with 1wt% of a surfactant and a pH regulator, wherein the pH value of the sodium hypochlorite solution is 5.
2. The method for preparing the nano-silica grafted halamine antibacterial melt-blown material according to claim 1, which is characterized in that: the mass ratio of the nano silicon dioxide grafted N-halamine precursor powder to the melt-blown polypropylene resin in the step S3 is (2-5) (80-100).
3. The method for preparing the nano-silica grafted halamine antibacterial melt-blown material according to claim 1, which is characterized in that: in the step S4, the surfactant is triton; the pH regulator is dilute sulfuric acid.
4. The method for preparing the nano-silica grafted halamine antibacterial melt-blown material according to claim 1, which is characterized in that: the mass ratio of the modified nano silicon dioxide to the N-halamine precursor in the step S2 is (8-12): 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.
5. The method for preparing the nano-silica grafted halamine antibacterial melt-blown material according to claim 1, which is characterized in that: the melt blowing machine in the step S3 comprises four large heating sections, the temperature setting range is 180-240 ℃, the hot air flow temperature is 220-240 ℃, the hot air flow pressure is 0.1-0.3Mpa, the frequency of a main screw motor is 8-12Hz, the receiving distance is 20-30cm, and the rotating speed of a receiving roller is 75-85m/min.
6. A nano silicon dioxide grafted halamine antibacterial melt-blown material is characterized in that: is prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the nano-silica grafted haloamine antibacterial meltblown material prepared by the preparation method according to any one of claims 1 to 5 or the nano-silica grafted haloamine antibacterial meltblown material according to claim 6, 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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| KR102321626B1 (en) * | 2014-10-21 | 2021-11-04 | 어번 유니버시티 | N-halamine containing fibrous compositions and uses thereof |
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