CN113279147A - Graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth and preparation method thereof - Google Patents

Graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth and preparation method thereof Download PDF

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CN113279147A
CN113279147A CN202110511298.2A CN202110511298A CN113279147A CN 113279147 A CN113279147 A CN 113279147A CN 202110511298 A CN202110511298 A CN 202110511298A CN 113279147 A CN113279147 A CN 113279147A
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graphene oxide
melt
filter cloth
modified high
isocyanate
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吕莉
薛冬梅
杨希舜
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Hua Bida Science And Technology Ltd S Of Shenzhen
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Hua Bida Science And Technology Ltd S Of Shenzhen
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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
    • D04H1/542—Adhesive fibres
    • D04H1/544—Olefin series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing

Abstract

The invention relates to the technical field of environment-friendly filter materials, in particular to a graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth which is prepared by melt-blowing, wherein a polypropylene main chain is not modified, therefore, the polypropylene non-woven fabric obtained by melt-blowing still keeps better air permeability and filtering performance, and by a quadruple hydrogen bond self-assembly mode that the strength between two ureido pyrimidinones is approximate to that of a covalent bond, the graphene oxide with good antibacterial performance is grafted in the polypropylene non-woven fabric, the agglomeration of the graphene oxide is inhibited under the action of quadruple hydrogen bonds, the mechanical property of the non-woven fabric is improved, and due to the presence of the quadruple hydrogen bonds, therefore, the polypropylene non-woven fabric has stronger mechanical property and certain self-repairing property, so that the non-woven fabric can be repeatedly washed and still has better filtering property and antibacterial property after being recycled.

Description

Graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth and preparation method thereof
Technical Field
The invention relates to the technical field of environment-friendly filter materials, in particular to a graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth and a preparation method thereof.
Background
With the development of the technology, various materials with specificity to the traditional materials are produced, the non-woven fabric is a material different from the traditional textile fabric and is usually obtained by melt-blowing of raw materials such as polypropylene and the like, the non-woven fabric does not have larger pore space of common yarn woven fabric, the fiber fineness of the non-woven fabric is low, the structure is fluffy, the pores are rich, the pore size is small, and the non-woven fabric has very good filtering performance, so the non-woven fabric is often used as a filtering material in an air conditioner, a ventilation fan, a dust remover and a mask, wherein the mask is used as an air filtering material contacting with skin, not only good filtering performance but also good air permeability and protection capability are needed, so the mask is particularly important for carrying out antibacterial modification on the mask, and particularly for medical care personnel in a complex environment.
Graphene oxide is a nano material with a plurality of excellent properties, not only has good electrochemical properties, but also has good antibacterial properties, has a plurality of applications in the field of textiles at present, is an antibacterial additive material with a good prospect, and has a very high application potential when being used as a modified material for antibacterial materials of masks, but the graphene oxide is easily agglomerated by simple physical blending and adding of the graphene oxide, so that the defect of the non-woven fabric is formed, the filtering property of the non-woven fabric is influenced, and the problem can be well solved by a chemical grafting mode, so that the non-woven fabric keeps good filtering property and is endowed with antibacterial property.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth and the preparation method thereof, and solves the problem that the polypropylene non-woven filter cloth does not have antibacterial performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth comprises the following steps:
(1) adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-neck flask, charging nitrogen, heating for reflux reaction, washing precipitate, reflux extracting, and vacuum drying to obtain isocyanate-ureidopyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 20-30min, adding isocyanate ureidopyrimidone, carrying out ultrasonic treatment for 20-30min, adding dibutyltin dilaurate, heating, preserving heat, carrying out reaction, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone grafted graphene;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based ureidopyrimidone, performing ultrasonic dispersion, then adding dibutyltin dilaurate, heating for reaction, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureidopyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene, stirring and mixing, performing ultrasonic treatment, adding into a melt-blown spinning machine, and performing melt-blown spinning process to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
Preferably, the mass ratio of the 4, 4' -methylenebis (phenyl isocyanate) to the 2-amino-4-hydroxy-6-methylpyrimidine in the step (1) is 100: 8-14.
Preferably, the temperature of the reflux reaction in the step (1) is 90-120 ℃, and the reaction time is 16-24 h.
Preferably, the mass ratio of the graphene oxide, the isocyanate-based ureidopyrimidinone and the dibutyltin dilaurate in the step (2) is 100:2000-3000: 20-30.
Preferably, the reaction temperature in the step (2) is 40-50 ℃ and the reaction time is 36-72 h.
Preferably, in the step (4), the mass ratio of the hydroxyl-terminated polypropylene to the isocyanate-based urea-pyrimidone to the dibutyltin dilaurate is 100:40-60: 2-4.
Preferably, the heating in the step (4) is carried out at the temperature of 40-60 ℃ for 36-72 h.
Preferably, the mass ratio of the ureido pyrimidinone grafted polypropylene to the isocyanate ureido pyrimidinone in the step (5) is 100: 0.3-1.
Preferably, the parameters of the melt-blown spinning machine in the melt-blown spinning process in the step (5) are that the temperature of a die head is 180-.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
according to the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth, 4' -methylene bis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine are reacted to prepare isocyanate-ureido pyrimidone, hydroxy on graphene oxide is reacted with isocyanate groups on the isocyanate-ureido pyrimidone under the catalysis of dibutyltin dilaurate to obtain ureido pyrimidone grafted graphene, and diethyl zinc, triethyl aluminum and a catalyst TiCl are used as cocatalysts4、MgCl2The method comprises the steps of carrying out polymerization reaction on propylene under the catalysis of dibutyltin dilaurate, oxidizing to obtain hydroxyl-terminated polypropylene, reacting hydroxyl on the hydroxyl-terminated polypropylene with an isocyanate group under the catalysis of dibutyltin dilaurate to obtain ureidopyrimidone grafted polypropylene, finally carrying out melt blending and dispersion to enable quadruple hydrogen bonds to carry out self-assembly, and finally carrying out melt blowing to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter clothThe polypropylene non-woven fabric obtained by melt-blowing still keeps good air permeability and filtering performance, and is an excellent air filter material for products such as masks and the like.
The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth is grafted with graphene oxide in a polypropylene non-woven fabric in a quadruple hydrogen bond self-assembly mode that the strength between two ureido pyrimidinones is nearly covalent bond, the graphene oxide has good antibacterial performance and can destroy a phospholipid bilayer after contacting a bacterial cell membrane, so that cell death is caused and most of bacteria are killed, the graphene oxide can be firmly positioned in a polypropylene non-woven fabric matrix in the quadruple hydrogen bond assembly mode, the graphene oxide has physical antibacterial performance, so that the good antibacterial performance can be still kept in a repeated elution process, the occurrence of agglomeration of the graphene oxide is inhibited due to the action of the quadruple hydrogen bond, the graphene oxide has good mechanical performance and is well dispersed in the non-woven fabric, so that the material has good mechanical properties.
This antibacterial modified high strength of graphite alkene oxide melts and spouts non-woven fabrics, owing to introduced ureido pyrimidinone group on the polypropylene, can self-assembly quadruple hydrogen bond, because quadruple hydrogen bond intensity is very high, be close to the covalent bond, and can self-identification, still can self-identification repair after the fracture, thereby make the polypropylene non-woven fabrics have stronger mechanical properties and certain selfreparing performance, make the washing that the non-woven fabrics can relapse, still keep good structure after the cyclic utilization, and have better filtering quality and antibacterial property, satisfy the use under the general condition.
Drawings
FIG. 1 is a reaction scheme for the preparation of isocyanato-ureidopyrimidinones;
figure 2 is a schematic diagram of a self-assembled quadruple hydrogen bonding structure.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth comprises the following steps:
(1) adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-necked flask with the mass ratio of 100:8-14, charging nitrogen, carrying out reflux reaction for 16-24h at 90-120 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 20-30min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 20-30min, adding dibutyltin dilaurate, wherein the mass ratio of the graphene oxide to the isocyanate-based ureidopyrimidone to the dibutyltin dilaurate is 100:2000-3000:20-30, carrying out heat preservation reaction for 36-72h at the temperature of 40-50 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone grafted graphene;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based ureidopyrimidone, performing ultrasonic dispersion, then adding dibutyltin dilaurate, heating to 40-60:2-4 by mass ratio of 100:40-60:2-4, reacting for 36-72h, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureidopyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:0.3-1, stirring and mixing, performing ultrasonic treatment, and adding the mixture into a melt-blown spinning machine, wherein the parameters of the melt-blown spinning machine are that the temperature of a die head is 180-.
Example 1
(1) Adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-necked flask with the mass ratio of 100:8, charging nitrogen, carrying out reflux reaction for 16h at 90 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 20min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 20min, adding dibutyltin dilaurate, carrying out heat preservation reaction for 36h at 40 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone-grafted graphene, wherein the mass ratio of the graphene oxide to the isocyanate-ureido pyrimidone to the dibutyltin dilaurate is 100:2000: 20;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based urea pyrimidone, performing ultrasonic dispersion, adding dibutyltin dilaurate in a mass ratio of 100:40:2, heating to 40 ℃, reacting for 36 hours, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureido pyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:0.3, stirring and mixing, performing ultrasonic treatment, adding the mixture into a melt-blown spinning machine, setting the parameters of the melt-blown spinning machine as die head temperature 180 ℃, zone 1 temperature 190 ℃, zone 2 temperature 200 ℃, zone 3 temperature 200 ℃, and performing melt-blown spinning process to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
Example 2
(1) Adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-necked flask with the mass ratio of 100:10, charging nitrogen, carrying out reflux reaction for 18h at 100 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 25min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 25min, adding dibutyltin dilaurate, carrying out heat preservation reaction for 45h at the temperature of 45 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone-grafted graphene, wherein the mass ratio of the graphene oxide to the isocyanate-ureido pyrimidone to the dibutyltin dilaurate is 100:2300: 23;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based urea pyrimidone, performing ultrasonic dispersion, adding dibutyltin dilaurate in a mass ratio of 100:45:2.5, heating to 45 ℃, reacting for 45 hours, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureido pyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:0.5, stirring and mixing, performing ultrasonic treatment, adding the mixture into a melt-blown spinning machine, setting the parameters of the melt-blown spinning machine as die head temperature 190 ℃, 1 zone temperature 200 ℃, 2 zone temperature 210 ℃, 3 zone temperature 210 ℃, and performing melt-blown spinning process to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
Example 3
(1) Adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-neck flask with the mass ratio of 100:11, charging nitrogen, carrying out reflux reaction for 20h at 105 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 25min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 25min, adding dibutyltin dilaurate, carrying out heat preservation reaction for 54h at 45 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone-grafted graphene, wherein the mass ratio of the graphene oxide to the isocyanate-ureido pyrimidone to the dibutyltin dilaurate is 100:2500: 25;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based urea pyrimidone, performing ultrasonic dispersion, adding dibutyltin dilaurate in a mass ratio of 100:50:3, heating to 50 ℃, reacting for 54h, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureido pyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:0.7, stirring and mixing, performing ultrasonic treatment, adding the mixture into a melt-blown spinning machine, setting the parameters of the melt-blown spinning machine as die head temperature 190 ℃, 1 zone temperature 200 ℃, 2 zone temperature 210 ℃, 3 zone temperature 210 ℃, and performing melt-blown spinning process to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
Example 4
(1) Adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-neck flask with the mass ratio of 100:12, charging nitrogen, carrying out reflux reaction for 22h at 110 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 25min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 25min, adding dibutyltin dilaurate, carrying out heat preservation reaction for 63h at 45 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone-grafted graphene, wherein the mass ratio of the graphene oxide to the isocyanate-ureido pyrimidone to the dibutyltin dilaurate is 100:2800: 28;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based urea pyrimidone, performing ultrasonic dispersion, adding dibutyltin dilaurate in a mass ratio of 100:55:3.5, heating to 55 ℃, reacting for 63 hours, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureido pyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:0.85, stirring and mixing, performing ultrasonic treatment, adding into a melt-blown spinning machine, setting the parameters of the melt-blown spinning machine as die head temperature 190 ℃, 1 zone temperature 200 ℃, 2 zone temperature 210 ℃, 3 zone temperature 210 ℃, and performing melt-blown spinning to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
Example 5
(1) Adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-necked flask with the mass ratio of 100:14, charging nitrogen, carrying out reflux reaction for 24 hours at 120 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 30min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 30min, adding dibutyltin dilaurate, carrying out heat preservation reaction for 72h at 50 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone-grafted graphene, wherein the mass ratio of the graphene oxide to the isocyanate-ureido pyrimidone to the dibutyltin dilaurate is 100:3000: 30;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based urea pyrimidone, performing ultrasonic dispersion, adding dibutyltin dilaurate in a mass ratio of 100:60:4, heating to 60 ℃, reacting for 72 hours, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureido pyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:1, stirring and mixing, performing ultrasonic treatment, adding the mixture into a melt-blown spinning machine, setting the parameters of the melt-blown spinning machine as die head temperature 200 ℃, zone 1 temperature 210 ℃, zone 2 temperature 220 ℃, zone 3 temperature 220 ℃, and performing melt-blown spinning to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
Comparative example 1
(1) Adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-necked flask with the mass ratio of 100:6, charging nitrogen, carrying out reflux reaction for 16h at 90 ℃, precipitating, washing, reflux extracting and vacuum drying to obtain isocyanate-ureido pyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 20min, adding isocyanate-based ureidopyrimidone, carrying out ultrasonic treatment for 20min, adding dibutyltin dilaurate, carrying out heat preservation reaction for 36h at 40 ℃, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone-grafted graphene, wherein the mass ratio of the graphene oxide to the isocyanate-ureido pyrimidone to the dibutyltin dilaurate is 100:1700: 17;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based urea pyrimidone, performing ultrasonic dispersion, adding dibutyltin dilaurate in a mass ratio of 100:35:1.5, heating to 40 ℃, reacting for 36h, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureido pyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene according to the mass ratio of 100:0.3, stirring and mixing, performing ultrasonic treatment, adding the mixture into a melt-blown spinning machine, setting the parameters of the melt-blown spinning machine as die head temperature 180 ℃, zone 1 temperature 190 ℃, zone 2 temperature 200 ℃, zone 3 temperature 200 ℃, and performing melt-blown spinning process to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
The nonwoven filter cloths of the examples and comparative examples were tested for air permeability using an SG461-III air permeameter.
Figure RE-GDA0003150055720000101
The non-woven filter cloth of the embodiment and the comparative example is cut into small round pieces with the diameter of 0.5cm and added into a conical flask, 5ml of staphylococcus aureus bacterial suspension and 70ml of phosphate buffer solution are respectively added, the mixture is fully contacted and shaken for 15min at 24 ℃, then 1ml of solution is extracted from each conical flask, 9ml of buffer solution is added for dilution, the mixture is cultured for 24h at 37 ℃ in agar culture medium, and the number of viable bacteria is calculated by a plate counting method by taking the small round pieces of common non-woven fabric as a control.
Figure RE-GDA0003150055720000102
Figure RE-GDA0003150055720000111
The nonwoven filter cloths of the examples and comparative examples were tested for tensile strength using a HF9011 universal tester.
Figure RE-GDA0003150055720000112

Claims (9)

1. The utility model provides an antibiotic modified high strength of oxidation graphite alkene melts and spouts nonwoven filter cloth which characterized in that: the preparation method of the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth comprises the following steps:
(1) adding 4, 4' -methylenebis (phenyl isocyanate) and 2-amino-4-hydroxy-6-methylpyrimidine into a three-neck flask, charging nitrogen, heating for reflux reaction, washing precipitate, reflux extracting, and vacuum drying to obtain isocyanate-ureidopyrimidinone;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 20-30min, adding isocyanate ureidopyrimidone, carrying out ultrasonic treatment for 20-30min, adding dibutyltin dilaurate, heating, preserving heat, carrying out reaction, washing with acetone, carrying out centrifugal separation, and carrying out vacuum drying to obtain ureidopyrimidone grafted graphene;
(3) diethyl zinc, triethyl aluminum and TiCl are sequentially added4、MgCl2Adding the mixture into a toluene solvent, introducing propylene gas, heating for polymerization reaction, drying oxygen for oxidation reaction, adding hydrochloric acid for quenching reaction, standing for liquid separation, distilling, washing, and vacuum drying to obtain hydroxyl-terminated polypropylene;
(4) adding hydroxyl-terminated polypropylene into a toluene solvent, adding isocyanate-based ureidopyrimidone, performing ultrasonic dispersion, then adding dibutyltin dilaurate, heating for reaction, evaporating to remove the solvent, washing with absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain ureidopyrimidone grafted polypropylene;
(5) heating and melting ureido pyrimidone grafted polypropylene, adding ureido pyrimidone grafted graphene, stirring and mixing, performing ultrasonic treatment, adding into a melt-blown spinning machine, and performing melt-blown spinning process to obtain the graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth.
2. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: in the step (1), the mass ratio of the 4, 4' -methylene bis (phenyl isocyanate) to the 2-amino-4-hydroxy-6-methylpyrimidine is 100: 8-14.
3. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: the temperature of the reflux reaction in the step (1) is 90-120 ℃, and the reaction time is 16-24 h.
4. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: the mass ratio of the graphene oxide, the isocyanate-based ureido pyrimidone and the dibutyltin dilaurate in the step (2) is 100:2000-3000: 20-30.
5. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: in the step (2), the temperature for heating and heat preservation for reaction is 40-50 ℃, and the reaction time is 36-72 h.
6. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: the mass ratio of the hydroxyl-terminated polypropylene, the isocyanate-based urea pyrimidone and the dibutyltin dilaurate in the step (4) is 100:40-60: 2-4.
7. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: the temperature for heating and reacting in the step (4) is 40-60 ℃, and the reaction time is 36-72 h.
8. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: the mass ratio of the ureido pyrimidone grafted polypropylene to the isocyanate ureido pyrimidone in the step (5) is 100: 0.3-1.
9. The graphene oxide antibacterial modified high-strength melt-blown non-woven filter cloth according to claim 1, which is characterized in that: the parameters of the melt-blown spinning machine in the melt-blown spinning process in the step (5) are that the temperature of a die head is 180-.
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CN110694351A (en) * 2019-10-23 2020-01-17 南通强生石墨烯科技有限公司 Antibacterial graphene composite filter screen and application thereof
CN111484597A (en) * 2020-04-16 2020-08-04 广州市白云化工实业有限公司 Modified polyurethane prepolymer, bi-component polyurethane adhesive and preparation method thereof

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US5307796A (en) * 1990-12-20 1994-05-03 Minnesota Mining And Manufacturing Company Methods of forming fibrous filtration face masks
CN106178691A (en) * 2016-09-06 2016-12-07 安徽丰磊制冷工程有限公司 A kind of polypropylene electret air filting material containing graphene oxide and preparation method thereof
CN110694351A (en) * 2019-10-23 2020-01-17 南通强生石墨烯科技有限公司 Antibacterial graphene composite filter screen and application thereof
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