CN114000261B - Preparation method of medical non-woven fabric and product thereof - Google Patents

Preparation method of medical non-woven fabric and product thereof Download PDF

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CN114000261B
CN114000261B CN202111468418.1A CN202111468418A CN114000261B CN 114000261 B CN114000261 B CN 114000261B CN 202111468418 A CN202111468418 A CN 202111468418A CN 114000261 B CN114000261 B CN 114000261B
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woven fabric
slurry
preparing
rubber roll
grinding
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CN114000261A (en
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崔大祥
陈超
王敬锋
林琳
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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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
    • 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
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • 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
    • D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Materials For Medical Uses (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention discloses a preparation method of medical non-woven fabric and a product thereof, which comprises the steps of preparing a fluorine-containing acrylic acid prepolymer in a viscous liquid state by utilizing polymerization reaction, then mixing the fluorine-containing acrylic acid prepolymer with a photoinitiator, an antibacterial resin and a thermoplastic resin component into polyvinylidene fluoride/dimethylformamide solution for premixing, grinding the mixture into slurry with high fineness by using a low-temperature wet grinding process, and well dispersing reaction components and functional components. By means of the mechanism of electrostatic spinning, the slurry is sprayed to a metal substrate covered by the non-woven fabric into filaments through strong electric field force, the non-woven fabric base is comprehensively and uniformly covered by fibers through controlling the moving speed of the non-woven fabric in the horizontal direction, and the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function is obtained through photocuring treatment.

Description

Preparation method of medical non-woven fabric and product thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of medical non-woven fabric and a product thereof.
Background
The non-woven fabric is a new-generation environment-friendly material, and has the advantages of good strength, air permeability, water resistance, environmental friendliness, flexibility, no toxicity, no odor, low price and the like. It is a new generation environment-friendly material, and has the characteristics of water repellency, ventilation, flexibility, no combustion supporting, no toxicity, no irritation, rich colors and the like.
Nonwoven fabrics are produced by a number of processes, such as spunlace, in which high pressure fine water jets are directed onto one or more fibrous webs to entangle the fibers with each other, thereby consolidating the webs with a certain strength. The heat-seal non-woven refers to that fibrous or powdery hot-melt adhesive reinforcing material is added into a fiber web, and the fiber web is heated, melted and cooled to be reinforced into cloth. The air-laid non-woven fabric is also called dustless paper and dry paper-making non-woven fabric, and is made up by using air-laid technique to open the wood pulp fibre board into single fibre state, then using air-laid method to make the fibre be coagulated on the net-forming curtain, then using the fibre net to make the fibre net be consolidated into the cloth. Wet non-woven is that fibrous material put in water medium is opened into single fiber, different fibrous materials are mixed together to make into fiber suspension pulp, the suspension pulp is delivered to web-forming tissue, the fiber is web-formed under wet state and then consolidated into cloth. Spunbond nonwoven fabrics are nonwoven fabrics formed by extruding and drawing a polymer to form continuous filaments, laying the filaments into a web, and then bonding, thermally bonding, chemically bonding, or mechanically reinforcing the web by itself. Skill course of melt-blown nonwoven: polymer feeding-melt extrusion-fiber formation-fiber cooling-web formation-reinforcement into cloth. One type of needle-punched non-woven dry-process non-woven fabric is a fabric that is reinforced with a loose web using the piercing action of a needle. Stitchbonded nonwovens use a warp knit loop construction to reinforce webs, layers of yarn, nonwoven materials (e.g., plastic sheets, plastic foil, etc.), or combinations thereof to form a nonwoven.
The non-woven fabrics have various purposes, and particularly have less chance in the medical and health fields, and the medical and sanitary non-woven fabrics mainly comprise operating gowns, protective clothing, disinfection wrapping cloth, masks, diapers, civil cleaning rags, wiping cloth, wet tissues, magic towels, soft towel rolls, beauty products, sanitary towels, sanitary protection pads, disposable sanitary cloth and the like. In order to further meet the special requirements of hospitals, such as antibiosis, reduction of wound skin adhesion and certain thermoplastic setting (similar to splint plaster) performance, the development of the medical non-woven fabric preparation technology is carried out.
Disclosure of Invention
The invention aims to provide a preparation method of medical non-woven fabric.
Yet another object of the present invention is to: provides a medical non-woven fabric product prepared by the method.
The purpose of the invention is realized by the following scheme: a preparation method of medical non-woven fabric, which utilizes an electrostatic spinning process to prepare thermoplastic composite medical non-woven fabric with hydrophobic and oleophobic antibacterial function, comprises the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: taking 10-20 parts by mass of hexafluorobutyl acrylate, 13 parts by mass of hydroxyethyl acrylate, 12 parts by mass of butyl acrylate and 5 parts by mass of chain transfer agent n-dodecyl disulfide into 150 parts by mass of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, and dissolving 50 parts by mass of hexafluorobutyl acrylate, 13 parts by mass of hydroxyethyl acrylate, 12 parts by mass of butyl acrylate and 5 parts by mass of chain transfer agent n-dodecyl disulfide into the solution5 parts of 1,4-dioxane of azodiisobutyronitrile initiator are slowly dripped into the mixture to react until the product reaches 1640cm -1 、810cm -1 Stopping reaction after an infrared absorption peak of a double bond at the position disappears, removing a solvent through rotary evaporation, drying, dissolving a product in 250 parts of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30 parts of triethylamine, stirring and mixing uniformly, slowly dripping 5 parts of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until a hydroxyl infrared absorption peak disappears, removing volatile components such as ethyl acetate and the like through rotary evaporation, and finally drying in vacuum at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing the prepolymer electro-spinning slurry: weighing 15 parts of fluorine-containing acrylate prepolymer, 0.3 part of photoinitiator 2-hydroxy-2 methyl-1 phenyl-1 acetone, 0.15 part of 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate, 30 parts of polycaprolactone powder and 5 parts of nano zinc oxide by mass, adding the mixture into 1000-1500 parts of polyvinylidene fluoride/dimethylformamide solution with mass concentration of 15%, premixing, and filling the mixture into wet grinding equipment, wherein the grinding medium is zirconium oxide microspheres, the grinding speed is 2000rpm, the temperature of the material during grinding is controlled below 3 ℃, and when the particle size D of particles in the material is smaller than the set value 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain the prepolymer electrospinning slurry.
Step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning liquid into a sizing tank, wherein the addition amount is preferably 3-5mm when the bottom of a rubber roll is submerged into the sizing agent, simultaneously connecting a sizing agent feeding circulation system of a peristaltic pump, and rotationally sizing the rubber roll at a proper rotating speed by connecting a high voltage. After the non-woven fabric is unreeled, the non-woven fabric is tightly attached to a pole plate right above the rubber roller to perform horizontal uniform-speed reeling motion, slurry at the upper end of the rubber roller upwards forms jet flow under the action of high-voltage electrostatic field force, and the jet flow is uniformly deposited on the non-woven fabric above to form fiber-covered and interwoven composite non-woven fabric. The composite non-woven fabric is photopolymerized by a high-pressure mercury lamp with the illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
The diameter of the grinding medium zirconia microspheres used in the wet grinding is less than or equal to 0.1mm.
As described aboveThe gram weight of the non-woven fabric is 10 to 20g/m 2 。
A plurality of parallel rubber rollers can be simultaneously placed in the sizing trough during spinning, the rubber rollers have the same specification, can be simultaneously electrified for rotary sizing, and the rotating direction can be independently controlled.
The voltage range of the spinning is 70 to 100KV, the distance h from the upper end of the rubber roll to the polar plate is 170 to 200mm, the winding speed of the non-woven fabric is 0.2 to 1m/s, the environmental temperature of the spraying space is 40 to 50 ℃, and the humidity is 40 to 60 percent.
The molecular weight of the polycaprolactone PCL used in the method is 50000-80000, the melting point is more than or equal to 60 ℃, and the usable resin powder is obtained through a low-temperature grinding means.
The invention provides a medical non-woven fabric prepared by any one of the methods, the obtained composite medical non-woven fabric is easy to soften for plasticity at the temperature of more than 60 ℃ (heated by hot water or a hair drier), the shapes of a film and a sheet can keep certain stability when the temperature is lower than 50 ℃, and the two forms are reversible according to temperature change. Meanwhile, the contact angle of the non-woven fabric to oil and water is larger than 90 degrees.
The finally obtained medical non-woven fabric has the antibacterial rate of more than or equal to 99 percent on staphylococcus aureus and escherichia coli, the air resistance of less than 90Pa and good air permeability.
The invention firstly utilizes polymerization reaction to prepare fluorine-containing acrylic acid prepolymer in a viscous liquid state, then mixes the prepolymer with photoinitiator, antibacterial and thermoplastic resin components and polyvinylidene fluoride/dimethylformamide solution for premixing, and then grinds the prepolymer into slurry with high fineness by a low-temperature wet grinding process, and reaction components and functional components can be well dispersed. By means of the mechanism of electrostatic spinning, the slurry is sprayed to a metal substrate covered by the non-woven fabric into filaments through strong electric field force, the non-woven fabric base is comprehensively and uniformly covered by fibers through controlling the moving speed of the non-woven fabric in the horizontal direction, and the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function is obtained through photocuring treatment.
Drawings
FIG. 1: the invention has a simple process flow;
the reference numbers in the figures illustrate:
1-electrospinning slurry; 2-gluing groove; 3-rubber roller;
4-peristaltic pump slurry feeding circulation system; 5-non-woven fabrics; 6-pole plate;
7-unwinding the reel; 8-tensioning shaft; 9-passing through the reel;
10-light curing box.
Detailed Description
The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1:
a medical non-woven fabric is prepared by an electrostatic spinning process, and the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function is prepared by the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: 10g of hexafluorobutyl acrylate, 13g of hydroxyethyl acrylate, 12g of butyl acrylate and 5g of chain transfer agent n-dodecyl mercaptan are dissolved in 150g of 1,4-dioxane, the mixture is stirred, refluxed and heated to 85 ℃ in a nitrogen atmosphere, 50g of 1,4-dioxane in which 5g of azobisisobutyronitrile initiator is dissolved is slowly dripped into the mixture for reaction, and when a product reaches 1640cm -1 、810cm -1 Stopping reaction after an infrared absorption peak of a double bond at the position disappears, removing a solvent through rotary evaporation, drying, dissolving a product in 250g of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30g of triethylamine, stirring and mixing uniformly, slowly dripping 5g of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until a hydroxyl infrared absorption peak disappears, removing volatile components such as ethyl acetate and the like through rotary evaporation, and finally drying in vacuum at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing electrospinning slurry: taking 15g of fluorine-containing acrylate prepolymer, 0.3g of 2-hydroxy-2 methyl-1 phenyl-1 acetone as a photoinitiator, 0.15 g of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 30g of polycaprolactone powder and 5g of nano zinc oxide, adding 1000g of polyvinylidene fluoride with the mass concentration of 15%Premixing in dimethylformamide solution, and filling into wet grinding equipment, wherein the grinding medium is zirconia microsphere with diameter less than or equal to 0.1mm, the grinding speed is 2000rpm, the temperature of the material during grinding is controlled below 3 deg.C, and when the particle diameter D of the particles in the material 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: as shown in figure 1, adding an electrospinning slurry 1 into a sizing tank 2, wherein the addition amount is that the roller bottom of a rubber roller 3 is immersed in the slurry for 3-5 mm, simultaneously, a peristaltic pump slurry supplementing circulation system 4 is connected, the rubber roller 3 is connected with high voltage and rotates at a proper rotating speed for sizing, a non-woven fabric 5 is unreeled from an unreeling shaft 7, is tensioned by a tensioning shaft 8 and a reeling shaft and then is tightly attached to a polar plate 6 right above the rubber roller 3 for horizontal and uniform reeling, the slurry at the upper end of the rubber roller 3 upwards forms jet flow under the action of high-pressure electrostatic field force and is uniformly deposited on the non-woven fabric above to form a composite non-woven fabric with fiber covering interweaving, and the gram weight of the non-woven fabric is 10-20g/m 2 (ii) a The composite nonwoven fabric was photopolymerized with a high-pressure mercury lamp in a photocuring chamber 10 at an illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
Wherein, according to the production scale, more than two rubber rollers which are parallel to each other can be simultaneously placed in the sizing tank 2 during spinning, the specifications of the rubber rollers are the same, the rubber rollers are simultaneously electrified for rotary sizing, and the rotating direction is independently controlled.
The voltage range during spinning is 70 to 100KV, the distance h from the upper end of the rubber roll to the pole plate is 170 to 200mm, the winding speed of the non-woven fabric is 0.2 to 1m/s, the environmental temperature of a spraying space is 40 to 50 ℃, and the humidity is 40 to 60 percent.
The molecular weight of the polycaprolactone PCL is 50000-80000, the melting point is more than or equal to 60 ℃, and the usable resin powder is obtained by a low-temperature crushing method.
The results of the nonwoven related tests are shown in table 1: 99.4 percent of antibacterial rate of escherichia coli, 99.0 percent of antibacterial rate of staphylococcus aureus, 92 degrees of hydrophobic angle and 75pa of air resistance.
Example 2
A medical nonwoven fabric, similar to the procedure of example 1, prepared by the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: taking 15g of hexafluorobutyl acrylate, 13g of hydroxyethyl acrylate, 12g of butyl acrylate and 5g of chain transfer agent n-dodecyl mercaptan, dissolving in 150g of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, slowly dropping 50g of 1,4-dioxane dissolved with 5g of azodiisobutyronitrile initiator into the mixture for reaction, and waiting for the product to be 1640cm -1 、810cm -1 Stopping reaction after an infrared absorption peak of the double bond disappears, removing a solvent through rotary evaporation, drying, dissolving a product in 250g of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30g of triethylamine, stirring and mixing uniformly, slowly and dropwise adding 5g of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until a hydroxyl infrared absorption peak disappears, removing volatile components such as ethyl acetate through rotary evaporation, and finally drying in vacuum at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing electrospinning slurry: taking 15g of fluorine-containing acrylate prepolymer, 0.3g of photoinitiator 2-hydroxy-2 methyl-1 phenyl-1 acetone and 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester 0.15 g, 30g of polycaprolactone powder and 5g of nano zinc oxide, adding the mixture into 1300g of polyvinylidene fluoride/dimethylformamide solution with mass concentration of 15%, premixing, and filling the mixture into wet grinding equipment, wherein grinding media are zirconium oxide microspheres, the grinding speed is 2000rpm, the temperature of the material during grinding is controlled below 3 ℃, and when the particle size D in the material is below 3 DEG 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning slurry into a sizing tank, wherein the electrostatic spinning equipment is the same as that in the embodiment 1, the addition amount is preferably 3-5 mm when the bottom of a rubber roll is immersed into the slurry, meanwhile, a peristaltic pump slurry feeding circulation system is connected, the rubber roll is connected with high voltage and rotates at a proper rotating speed for sizing, the non-woven fabric is tightly attached to a polar plate right above the rubber roll after being unreeled to perform horizontal uniform rolling action, the slurry at the upper end of the rubber roll upwards forms jet flow under the action of high-voltage electrostatic field force, and the slurry is uniformly deposited on the non-woven fabric above to form fiber-covered and interwoven composite non-woven fabric; the composite non-woven fabric is photopolymerized by a high-pressure mercury lamp,illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
The results of the nonwoven related tests are shown in table 1: 99.3 percent of antibacterial rate of escherichia coli, 99.1 percent of antibacterial rate of staphylococcus aureus, 93 degrees of hydrophobic angle and 85pa of air resistance.
Example 3:
a medical nonwoven fabric, similar to the procedure of example 1, prepared by the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: dissolving 20g of hexafluorobutyl acrylate, 13g of hydroxyethyl acrylate, 12g of butyl acrylate and 5g of chain transfer agent n-dodecyl mercaptan into 150g of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, slowly dropping 50g of 1,4-dioxane dissolved with 5g of azodiisobutyronitrile initiator into the mixture for reaction, and waiting for the product to be 1640cm -1 、810cm -1 Stopping reaction after an infrared absorption peak of a double bond at the position disappears, removing a solvent through rotary evaporation, drying, dissolving a product in 250g of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30g of triethylamine, stirring and mixing uniformly, slowly dripping 5g of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until a hydroxyl infrared absorption peak disappears, removing volatile components such as ethyl acetate and the like through rotary evaporation, and finally drying in vacuum at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing electrospinning slurry: taking 15g of fluorine-containing acrylate prepolymer, 0.3g of 2-hydroxy-2 methyl-1 phenyl-1 acetone photoinitiator and 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester 0.15 g, 30g of polycaprolactone powder and 5g of nano zinc oxide, adding the materials into 1500g of polyvinylidene fluoride/dimethylformamide solution with the mass concentration of 15%, premixing the materials, and filling the materials into wet grinding equipment, wherein grinding media are zirconium oxide microspheres, the grinding speed is 2000rpm, the temperature of the materials during grinding is controlled below 3 ℃, and when the particle size D in the materials is 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning slurry into a sizing tankIn the method, electrostatic spinning equipment is the same as that in the embodiment 1, the addition amount is preferably 3 to 5mm when slurry is immersed into the bottom of a rubber roll, a slurry replenishing circulation system of a peristaltic pump is connected at the same time, the rubber roll is connected with high voltage and rotates at a proper rotating speed for sizing, a non-woven fabric is tightly attached to a pole plate right above the rubber roll after being unreeled to perform horizontal uniform-speed rolling action, the slurry at the upper end of the rubber roll upwards forms jet flow under the action of high-voltage electrostatic field force, and the jet flow is uniformly deposited on the non-woven fabric above to form fiber-covered and interwoven composite non-woven fabric; the composite non-woven fabric is photopolymerized by a high-pressure mercury lamp with the illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
The results of the nonwoven fabric-related tests are shown in Table 1, and the antibacterial rate of Escherichia coli is 99.5%. 99.0 percent of antibacterial rate of staphylococcus aureus, 91 degrees of hydrophobic angle and 71pa of air resistance
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Claims (10)

1. A preparation method of medical non-woven fabric is characterized in that an electrostatic spinning process is utilized to prepare thermoplastic composite medical non-woven fabric with amphiphobic antibacterial function, and comprises the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: taking 10-20 parts by mass of hexafluorobutyl acrylate, 13 parts of hydroxyethyl acrylate, 12 parts of butyl acrylate and 5 parts of chain transfer agent n-dodecyl disulfide into 150 parts of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, slowly dropping 50 parts of 1,4-dioxane dissolved with 5 parts of azodiisobutyronitrile initiator into the solution for reaction, and waiting for the product to be 1640cm -1 、810cm -1 Stopping reaction after infrared absorption peaks of double bonds at the position disappear, removing a solvent through rotary evaporation, drying, dissolving a product in 250 parts of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30 parts of triethylamine, stirring and mixing uniformly, slowly dripping 5 parts of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until infrared absorption peaks of hydroxyl groups disappear, removing volatile components of the ethyl acetate through rotary evaporation,finally, vacuum drying at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing electrospinning slurry: weighing 15 parts of fluorine-containing acrylate prepolymer, 0.3 part of photoinitiator 2-hydroxy-2 methyl-1 phenyl-1 acetone, 0.15 part of 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate, 30 parts of polycaprolactone powder and 5 parts of nano zinc oxide by mass, adding the components into 1000 to 1500 parts of polyvinylidene fluoride/dimethyl formamide solution with mass concentration of 15%, premixing, filling the mixture into wet grinding equipment, wherein the grinding medium is zirconium oxide microspheres, the grinding speed is 2000rpm, the temperature of the material during grinding is controlled below 3 ℃, and when the particle size D of particles in the material is smaller than the particle size D of the particles 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning slurry into a sizing tank, wherein the addition amount is 3-5 mm when the bottom of a rubber roll is immersed in the slurry, simultaneously connecting a slurry feeding circulation system of a peristaltic pump, connecting the rubber roll with high voltage, rotating the rubber roll at a proper rotating speed for sizing, after unreeling, tightly adhering a non-woven fabric to a polar plate right above the rubber roll to perform horizontal uniform-speed rolling action, forming a jet flow by the slurry at the upper end of the rubber roll under the action of high-voltage electrostatic field force, and uniformly depositing the slurry on the non-woven fabric above to form a fiber-covered and interwoven composite non-woven fabric; the composite non-woven fabric is photopolymerized by a high-pressure mercury lamp with the illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
2. The method for preparing the medical non-woven fabric according to claim 1, wherein the diameter of the grinding medium zirconia microspheres used for wet grinding is less than or equal to 0.1mm.
3. The method for preparing the medical non-woven fabric according to claim 1, wherein the gram weight of the non-woven fabric is 10 to 20g/m 2 。
4. The method for preparing medical non-woven fabric according to claim 1, wherein more than two parallel rubber rollers are simultaneously placed in the sizing tank during spinning, the rubber rollers have the same specification, are simultaneously electrified for sizing in a rotating manner, and are independently controlled in rotating direction.
5. The method for preparing the medical non-woven fabric according to claim 1, wherein the voltage range during spinning is 70 to 100KV, the distance h from the upper end of the rubber roll to the polar plate is 170 to 200mm, the winding speed of the non-woven fabric is 0.2 to 1m/s, the environmental temperature of a spraying space is 40 to 50 ℃, and the humidity is 40 to 60 percent.
6. The preparation method of the medical non-woven fabric according to claim 1, wherein the molecular weight of the polycaprolactone PCL is 50000 to 80000, the melting point is more than or equal to 60 ℃, and the usable resin powder is obtained through low-temperature grinding.
7. The method for preparing a medical nonwoven fabric according to any one of claims 1 to 6, characterized by comprising the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: taking 10g of hexafluorobutyl acrylate, 13g of hydroxyethyl acrylate, 12g of butyl acrylate and 5g of chain transfer agent n-dodecyl mercaptan, dissolving into 150g of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, slowly dropping 50g of 1,4-dioxane dissolved with 5g of azodiisobutyronitrile initiator into the mixture for reaction, and waiting for the product to be 1640cm -1 、810cm -1 Stopping reaction after an infrared absorption peak of the double bond disappears, removing a solvent through rotary evaporation, drying, dissolving a product in 250g of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30g of triethylamine, stirring and mixing uniformly, slowly dripping 5g of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until a hydroxyl infrared absorption peak disappears, removing volatile components of ethyl acetate through rotary evaporation, and finally drying in vacuum at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing electrospinning slurry: taking 15g of fluorine-containing acrylate prepolymer, 0.3g of 2-hydroxy-2 methyl-1 phenyl-1 acetone as photoinitiator, 0.15 g of 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate, and polycaprolactone powderAdding 30g of g and 5g nano zinc oxide into 1000g of polyvinylidene fluoride/dimethylformamide solution with mass concentration of 15%, premixing, and filling into wet grinding equipment, wherein the grinding medium is zirconia microspheres, the grinding speed is 2000rpm, the temperature of the material during grinding is controlled below 3 ℃, and when the particle size D of particles in the material is smaller than that of particles in the material 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning slurry (1) into a sizing tank (2), wherein the addition amount is 3-5 mm when the bottom of a rubber roll (3) is immersed in the slurry, and simultaneously a peristaltic pump slurry feeding circulation system (4) is connected, the rubber roll (3) is connected with high voltage and rotates at a proper rotating speed for sizing, a non-woven fabric (5) is unreeled from an unreeling shaft (7), is tensioned by a tensioning shaft (8) and a reeling shaft (9) and then is tightly attached to a polar plate (6) right above the rubber roll (3) to horizontally roll at a constant speed, the slurry at the upper end of the rubber roll (3) upwards forms jet flow under the action of high-pressure electrostatic field force, and is uniformly deposited on the non-woven fabric above to form a composite non-woven fabric covered and interwoven by fibers; the composite non-woven fabric is photopolymerized by a high-pressure mercury lamp in a photocuring box (10), and the illumination intensity is 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
8. The method for preparing a medical nonwoven fabric according to any one of claims 1 to 6, characterized by comprising the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: taking 15g of hexafluorobutyl acrylate, 13g of hydroxyethyl acrylate, 12g of butyl acrylate and 5g of chain transfer agent n-dodecyl mercaptan, dissolving in 150g of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, slowly dropping 50g of 1,4-dioxane dissolved with 5g of azodiisobutyronitrile initiator into the mixture for reaction, and waiting for the product to be 1640cm -1 、810cm -1 Stopping reaction after infrared absorption peak of double bond disappears, removing solvent by rotary evaporation, drying, dissolving the product in 250g of ethyl acetate, stabilizing the system temperature at zero centigrade degree, adding 30g of triethylamine, stirring, mixing uniformly, slowly dripping 5g of acryloyl chloride into the reactor, and reactingHeating to room temperature after 2 hours, stopping the reaction until the infrared absorption peak of hydroxyl disappears, performing rotary evaporation to remove the volatile component of ethyl acetate, and finally performing vacuum drying at low temperature to obtain the fluorine-containing acrylate prepolymer in a viscous liquid state;
step two, preparing electrospinning slurry: taking 15g of fluorine-containing acrylate prepolymer, 0.3g of photoinitiator 2-hydroxy-2 methyl-1 phenyl-1 acetone and 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester 0.15 g, 30g of polycaprolactone powder and 5g of nano zinc oxide, adding the materials into 1300g of polyvinylidene fluoride/dimethylformamide solution with the mass concentration of 15%, premixing the materials, then filling the materials into wet grinding equipment, wherein the grinding medium is zirconium oxide microspheres, the grinding speed is 2000rpm, the temperature of the materials during grinding is controlled below 3 ℃, and when the particle diameter D of particles in the materials is below 3 DEG 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning slurry into a sizing tank, wherein the addition amount is 3-5 mm of slurry immersed into the bottom of a rubber roll, simultaneously connecting a slurry feeding circulation system of a peristaltic pump, connecting the rubber roll with high voltage, rotating the rubber roll at a proper rotating speed for sizing, after unreeling the non-woven fabric, tightly adhering the non-woven fabric to a polar plate right above the rubber roll to perform horizontal uniform rolling action, enabling the slurry at the upper end of the rubber roll to form jet flow upwards under the action of high-voltage electrostatic field force, and uniformly depositing the slurry on the non-woven fabric above to form fiber-covered and interwoven composite non-woven fabric; photopolymerization is carried out on the composite non-woven fabric by a high-pressure mercury lamp with the illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
9. The method for preparing a medical nonwoven fabric according to any one of claims 1 to 6, characterized by comprising the following steps:
step one, preparing a fluorine-containing acrylate prepolymer: dissolving 20g of hexafluorobutyl acrylate, 13g of hydroxyethyl acrylate, 12g of butyl acrylate and 5g of chain transfer agent n-dodecyl mercaptan into 150g of 1,4-dioxane, stirring, refluxing and heating to 85 ℃ in a nitrogen atmosphere, slowly dropping 50g of 1,4-dioxane dissolved with 5g of azodiisobutyronitrile initiator into the mixture for reaction, and waiting for a product 1640cm -1 、810cm -1 Stopping reaction after an infrared absorption peak of the double bond disappears, removing a solvent through rotary evaporation, drying, dissolving a product in 250g of ethyl acetate, stabilizing the temperature of the system at zero centigrade, adding 30g of triethylamine, stirring and mixing uniformly, slowly dripping 5g of acryloyl chloride into a reactor, reacting for 2 hours, gradually heating to room temperature, stopping reaction until a hydroxyl infrared absorption peak disappears, removing volatile components of ethyl acetate through rotary evaporation, and finally drying in vacuum at low temperature to obtain a viscous liquid fluorine-containing acrylate prepolymer;
step two, preparing electrospinning slurry: taking 15g of fluorine-containing acrylate prepolymer, 0.3g of photoinitiator 2-hydroxy-2 methyl-1 phenyl-1 acetone and 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester 0.15 g, 30g of polycaprolactone powder and 5g of nano zinc oxide, adding the materials into 1500g of polyvinylidene fluoride/dimethylformamide solution with mass concentration of 15%, premixing the materials, and then filling the materials into a wet grinding device, wherein grinding media are zirconium oxide microspheres, the grinding speed is 2000rpm, the temperature of the materials during grinding is controlled below 3 ℃, and when the particle size D in the materials is below 3 DEG 90 Discharging when the particle size is less than or equal to 0.5 mu m to obtain prepolymer electrospinning slurry;
step three, preparing the composite medical non-woven fabric through electrostatic spinning: adding the electrospinning slurry into a sizing tank, wherein the addition amount is 3-5 mm of slurry immersed into the bottom of a rubber roll, simultaneously connecting a slurry feeding circulation system of a peristaltic pump, connecting the rubber roll with high voltage, rotating the rubber roll at a proper rotating speed for sizing, after unreeling the non-woven fabric, tightly adhering the non-woven fabric to a polar plate right above the rubber roll to perform horizontal uniform rolling action, enabling the slurry at the upper end of the rubber roll to form jet flow upwards under the action of high-voltage electrostatic field force, and uniformly depositing the slurry on the non-woven fabric above to form fiber-covered and interwoven composite non-woven fabric; the composite non-woven fabric is photopolymerized by a high-pressure mercury lamp with the illumination intensity of 30mW/cm 2 And exposing for 2 minutes to obtain the thermoplastic composite medical non-woven fabric with the amphiphobic antibacterial function.
10. A medical non-woven fabric, which is characterized by being prepared according to any one of the methods of claims 1-9, the obtained composite medical non-woven fabric is easily softened and plasticized at a temperature of more than 60 ℃, the shape of the non-woven fabric is kept stable at a temperature of less than 50 ℃, the two forms are reversible according to temperature change, the hydrophobic angle of the non-woven fabric to oil and water is larger than 90 degrees, the antibacterial rate to staphylococcus aureus and escherichia coli is larger than or equal to 99 percent, and the air resistance is smaller than 90Pa.
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