Disclosure of Invention
The invention aims to provide a biological medical non-woven fabric based on nano fibers and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a kind of biomedical non-woven fabrics based on nanometer fiber, the said biomedical non-woven fabrics based on nanometer fiber mainly includes the first non-woven fabrics, second non-woven fabrics; the mass ratio of the first non-woven fabric to the second non-woven fabric is 1: 1; the first non-woven fabric and the second non-woven fabric are bonded through an adhesive.
The first non-woven fabric has super-strong water absorption capacity, the second non-woven fabric has stronger hydrophobic and anti-radiation capacity, and the biomedical non-woven fabric obtained by bonding the first non-woven fabric and the second non-woven fabric through the adhesive is very suitable for manufacturing medical protective clothing; the biomedical non-woven fabric prepared by utilizing the synergistic effect of the first non-woven fabric and the second non-woven fabric has the capabilities of phase change temperature regulation, moisture absorption, antibiosis, blood repellency and radiation resistance, can effectively resist the invasion of microorganisms and pathogens while improving the wearing comfort of medical personnel, and has practicability.
Preferably, the first nonwoven fabric comprises the following raw material components: the anti-bacterial microcapsule comprises, by weight, 18-28 parts of an anti-bacterial capsule, 20-30 parts of gelatin, 17-27 parts of chitosan, 20-30 parts of a phase-change thermoregulation microcapsule, 30-60 parts of acrylonitrile, 20-30 parts of acrylamide, 15-25 parts of polyethylene glycol, 8-14 parts of 8-hydroxyquinoline copper, 6-10 parts of acrylic acid, 10-15 parts of a zinc chloride salt solvent, 10-14 parts of an oxidant and 7-10 parts of a reducing agent; the oxidant is ammonium persulfate, and the reducing agent is sodium sulfite.
The fiber for manufacturing the first non-woven fabric is the fiber with a shell-core structure, firstly, the phase-change temperature-regulating microcapsule is specially added in the core layer liquid, so that the non-woven fabric has the phase-change temperature-regulating capacity, and the stuffiness feeling of medical personnel when wearing the protective clothing is effectively improved; secondly, 8-hydroxyquinoline copper is reduced into copper ions in a shell liquid by an oxidation-reduction reaction, polyacrylonitrile is generated by in-situ polymerization, a copper chain and a super-hydrophilic group are introduced to a side chain of a polyacrylonitrile macromolecule, modified polyacrylonitrile with antibacterial and water absorption properties is obtained, the modified polyacrylonitrile is introduced to acrylic acid and acrylamide, the acrylic acid and the acrylamide are copolymerized to form gel, the spinning property can be effectively improved by adding polyethylene glycol and the modified polyacrylonitrile, and a large number of hydrophilic groups are introduced, so that the prepared fiber shell surface contains a large number of hydrophilic groups, and the fiber shell has the advantages of high water absorption speed, good moisture regain and strong antibacterial ability; the alkali liquor is sodium hydroxide solution.
According to the invention, after the core-shell liquid and the shell liquid are coaxially spun into fibers, the fibers are placed in alkali liquor for etching to obtain the fibers A with rough and porous surfaces, and then the ethylene group on the surface of the antibacterial capsule is grafted to an acrylamide molecular chain on the surface of the fibers A by using the oxidizing agent and the reducing agent, so that the adhesion between the antibacterial capsule and the first fibers is enhanced, and the falling of the antibacterial capsule caused by friction in the wearing process is avoided.
The antibacterial capsule has the advantages that the nano particles and the freshener are mixed and coated by the ethyl cellulose, the obtained antibacterial capsule has good slow release capacity, the main components of the nano particles are seaweed dry powder and zinc oxide, the beta-D-mannuronic acid and the alpha-L-guluronic acid in the seaweed contain carboxyl and hydroxyl, zinc ions can be attracted to aggregate with the beta-D-mannuronic acid and the alpha-L-guluronic acid to form stable nano particles, the nano particles and the freshener with the antibacterial effect can be continuously released, and the antibacterial capsule has the effects of long-acting bacteriostasis, deodorization, pressure relief and refreshing.
Preferably, the second non-woven fabric comprises the following raw material components: by weight, 30-40 parts of modified ceramic, 40-60 parts of polyvinyl alcohol, 15-25 parts of pentanediol, 20-28 parts of hydrochloric acid, 10-14 parts of acetone, 10-14 parts of 3-mercaptopropylsiloxane, 8-10 parts of n-hexane, 8-10 parts of dodecafluoroheptyl methacrylate and 8-10 parts of 2, 2-dimethoxy-phenyl acetophenone;
preferably, the antibacterial capsule comprises the following raw material components: 10-20 parts of zinc nitrate, 20-28 parts of seaweed dry powder, 10-20 parts of sodium hydroxide, 30-50 parts of polyvinyl alcohol, 20-28 parts of ethyl cellulose, 18-28 parts of dichloromethane, 17-27 parts of acetone, 10-20 parts of a freshener and 15-18 parts of an emulsifier by weight;
preferably, the cooling agent is one or more of menthol, borneol and lemon essential oil;
preferably, the modified ceramic mainly comprises porous ceramic, yttrium chloride hexahydrate; the mass ratio of the porous ceramic to the yttrium chloride hexahydrate is (4-7): 4: 3; the porous ceramic is nano porous ceramic;
preferably, the raw material components of the adhesive are as follows: 35-45 parts of carboxymethyl starch, 40-60 parts of acrylamide and 20-30 parts of ammonium persulfate by weight;
the adhesive takes ammonium persulfate as an initiator, acrylamide is grafted on carboxymethyl starch to form a reticular macromolecule with high stability and linear spreading capacity, and the adhesive force and water absorption capacity of the carboxymethyl starch are greatly improved; because the adhesive contains acrylamide, the adhesive and the first non-woven fabric have better compatibility; the adhesive has negative charges, the second non-woven fabric has positive charges, and the adhesive and the second non-woven fabric can be better combined and cannot easily fall off through electrostatic interaction.
Preferably, the preparation method of the porous ceramic is as follows: adding polysiloxane into dimethylbenzene, stirring for dissolving, sequentially adding nano iron powder, lanthanum oxide, zirconium oxide and oxidation roll, ultrasonically dispersing for 6-10h, raising the temperature to 45-55 ℃, reacting for 30-40min, pressing into a blank, and obtaining porous ceramic under the nitrogen atmosphere;
according to the invention, the porous ceramic is prepared through the cracking reaction of nano iron powder and polysiloxane, lanthanum oxide, zirconium oxide and oxidation rolling with anti-radiation capability are particularly added in the process of preparing the porous ceramic, wherein the rolling ions contained in the oxidation rolling can also effectively reduce the thermal diffusion coefficient and the thermal conductivity of the porous ceramic, so that the porous ceramic is endowed with excellent heat insulation performance; and then sodium hydroxide is used as a precipitator, yttrium chloride hexahydrate is used as a main raw material to prepare a charging agent, the charging agent is covered on the porous ceramic to modify the porous ceramic, yttrium oxide is generated on the porous ceramic through high-temperature calcination, Y-O and Y-Si bonds exist between the yttrium oxide and the porous ceramic, the combination is firm and has stronger electropositivity, and the yttrium oxide can react with negatively charged microorganisms to inactivate the microorganisms and has stronger antibacterial and bactericidal properties.
According to the invention, modified ceramic is added into polyvinyl alcohol to increase the surface roughness of the second fiber and increase the hydrophobic capacity, pentanediol is used for crosslinking, a mercapto functional group is introduced through a silane coupling agent, the mercapto functional group and fluorine-containing acrylate generate a click chemical reaction, and a fluorine-containing long chain functional group is grafted onto a polyvinyl alcohol molecular chain and then is subjected to electrostatic spinning to prepare the second fiber with strong hydrophobic performance.
A preparation method of a biological medical non-woven fabric based on nano fibers comprises the following steps:
(1) preparing an adhesive;
(2) preparing a first nonwoven fabric;
A. preparing an antibacterial capsule;
B. preparing a nuclear layer liquid;
C. preparing a shell layer solution;
D. a synthetic fiber A;
E. etching;
F. preparing a first nonwoven fabric;
(3) preparing a second non-woven fabric;
A. preparing modified ceramic;
B. synthesizing a second fiber;
C. preparing a second non-woven fabric;
(4) bonding;
the method specifically comprises the following steps:
(1) preparing an adhesive: adding carboxymethyl starch into deionized water, stirring uniformly, gelatinizing at 50-60 deg.C for 45-65min, adding acrylamide, stirring, adjusting pH to 7.8-8.8, adding ammonium persulfate under nitrogen atmosphere, stirring for 3-7h to obtain adhesive;
(2) preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 75-85 ℃, continuously stirring for 1.5-3.5h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 10-15h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 1-2 hours to obtain a solution A;
c) placing ethyl cellulose in dichloromethane and acetone, stirring and dissolving, adding the solution A, the freshener and the emulsifier, stirring at the rotating speed of 800-;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at the rotating speed of 800r/min for 25-45min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 1-2h, adding a zinc chloride salt solvent, continuously stirring for 10-20min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 38-48 ℃, stirring for reacting for 1.5-2.5h, and standing for 18-24h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 1-3min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 30-50min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 3-5cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(3) preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 20-50min at the temperature of 80-100 ℃, adding porous ceramic, performing ultrasonic dispersion for 3-6h, taking out and drying, and calcining at the temperature of 650-950 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 78-90 deg.C for 10-20min, adding modified ceramic, reducing temperature to 75-65 deg.C, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 50-80min, adding fiber B, soaking to react for 2-4h, taking out, washing and drying by deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 3-6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 10-15h, taking out, placing under ultraviolet light to react for 30-60min, washing by ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 3-5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
(4) bonding: and bonding the first non-woven fabric and the second non-woven fabric together by using an adhesive to obtain the biomedical non-woven fabric.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds phase-change thermoregulation microcapsule into the core layer liquid of the first fiber, prepares the fiber A with super-hydrophilic performance by introducing a large amount of hydrophilic groups into the core layer liquid, and makes porous on the surface of the fiber A by using alkali liquor to increase the binding force between the fiber A and the antibacterial capsule; the spinning solution is modified by an electrochemical method, modified ceramic with anti-radiation and anti-bacterial capabilities is added to obtain second fibers with super-hydrophobic performance, the first non-woven fabric and the second non-woven fabric are bonded by a bonding agent to obtain the biomedical non-woven fabric with the capabilities of phase change temperature regulation, moisture absorption, antibiosis, blood repellency and radiation resistance, the wearing comfort of medical workers is improved, meanwhile, invasion of microorganisms and pathogens can be effectively resisted, and the practicability is very high.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing an adhesive: adding carboxymethyl starch into deionized water, stirring uniformly, gelatinizing at 50 ℃ for 45min, adding acrylamide, stirring, adjusting the pH value to 7.8, adding ammonium persulfate under the nitrogen atmosphere, keeping the temperature and stirring for 3h to obtain an adhesive;
(2) preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 75-85 ℃, continuously stirring for 1.5h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 10h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 1h to obtain a solution A;
c) dissolving ethyl cellulose in dichloromethane and acetone under stirring, adding solution A, algefacient and emulsifier, stirring at 800r/min, adding sodium sulfate, reducing rotation speed to 100r/min, and stirring for 5 hr to obtain antibacterial capsule solution;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 500r/min for 25min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 1h, adding a zinc chloride salt solvent, continuously stirring for 10min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 38 ℃, stirring for reacting for 1.5h, and standing for 18h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 1min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 30min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 3cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(3) preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 20min at 80 ℃, adding porous ceramic, performing ultrasonic dispersion for 3h, taking out and drying, and calcining at 650 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 78 ℃ for 10min, adding modified ceramic, reducing the temperature to 75 ℃, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring for reacting for 50min, adding fiber B, soaking for reacting for 2h, taking out, washing and drying with deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, performing ultrasonic dispersion for 3h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone for reacting for 10h, taking out, placing under ultraviolet light for reacting for 30min, washing with ethanol, and drying to obtain a second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into small sections of 3cm, and carrying out spunlace to prepare second non-woven fabrics;
(4) bonding: and bonding the first non-woven fabric and the second non-woven fabric together by using an adhesive to obtain the biomedical non-woven fabric.
The first non-woven fabric comprises the following raw material components: the antibacterial and heat-insulating material comprises, by weight, 18 parts of antibacterial capsules, 20 parts of gelatin, 17 parts of chitosan, 20 parts of phase-change and temperature-adjusting microcapsules, 30 parts of polyacrylonitrile, 20 parts of acrylamide, 15 parts of polyethylene glycol, 8 parts of 8-hydroxyquinoline copper, 6 parts of acrylic acid, 10 parts of a zinc chloride salt solvent, 10 parts of an oxidant and 7 parts of a reducing agent.
The second non-woven fabric comprises the following raw material components: the modified polyvinyl alcohol modified silicone oil comprises, by weight, 30 parts of modified ceramic, 40 parts of polyvinyl alcohol, 15 parts of pentanediol, 20 parts of hydrochloric acid, 10 parts of acetone, 10 parts of 3-mercaptopropylsiloxane, 8 parts of n-hexane, 8 parts of dodecafluoroheptyl methacrylate and 8 parts of 2, 2-dimethoxy-phenylacetophenone.
The antibacterial capsule comprises the following raw material components: the cooling agent comprises, by weight, 10 parts of zinc nitrate, 20 parts of seaweed dry powder, 10 parts of sodium hydroxide, 30 parts of polyvinyl alcohol, 20 parts of ethyl cellulose, 18 parts of dichloromethane, 17 parts of acetone, 10 parts of a cooling agent and 15 parts of an emulsifier.
The mass ratio of the porous ceramic to the yttrium chloride hexahydrate is 4: 4:3.
The adhesive comprises the following raw material components: 35 parts of carboxymethyl starch, 40 parts of acrylamide and 20 parts of ammonium persulfate;
example 2
(1) Preparing an adhesive: adding carboxymethyl starch into deionized water, stirring uniformly, gelatinizing at 55 ℃ for 50min, adding acrylamide, stirring, adjusting the pH value to 8.0, adding ammonium persulfate under the nitrogen atmosphere, keeping the temperature and stirring for 5h to obtain an adhesive;
(2) preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 80 ℃, continuously stirring for 2h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 13h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 1.5 hours to obtain a solution A;
c) dissolving ethyl cellulose in dichloromethane and acetone under stirring, adding solution A, freshener and emulsifier, stirring at 950r/min, adding sodium sulfate, reducing rotation speed to 105r/min, and stirring for 6 hr to obtain antibacterial capsule solution;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 650r/min for 30min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 1.5h, adding a zinc chloride salt solvent, continuously stirring for 15min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 43 ℃, stirring for reacting for 2.0h, and standing for 21h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 2min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 40min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 4cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(3) preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 20-50min at the temperature of 80-100 ℃, adding porous ceramic, performing ultrasonic dispersion for 3-6h, taking out and drying, and calcining at the temperature of 650-950 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 78-90 deg.C for 10-20min, adding modified ceramic, reducing temperature to 75-65 deg.C, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 50-80min, adding fiber B, soaking to react for 2-4h, taking out, washing and drying by deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 3-6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 10-15h, taking out, placing under ultraviolet light to react for 30-60min, washing by ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 3-5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
(4) bonding: and bonding the first non-woven fabric and the second non-woven fabric together by using an adhesive to obtain the biomedical non-woven fabric.
The first non-woven fabric comprises the following raw material components: the anti-bacterial microcapsule comprises, by weight, 18-28 parts of an anti-bacterial capsule, 20-30 parts of gelatin, 17-27 parts of chitosan, 20-30 parts of a phase-change thermoregulation microcapsule, 30-60 parts of polyacrylonitrile, 20-30 parts of acrylamide, 20 parts of polyethylene glycol, 12 parts of 8-hydroxyquinoline copper, 8 parts of acrylic acid, 12 parts of a zinc chloride salt solvent, 12 parts of an oxidant and 8 parts of a reducing agent.
The second non-woven fabric comprises the following raw material components: the modified ceramic comprises, by weight, 35 parts of modified ceramic, 50 parts of polyvinyl alcohol, 20 parts of pentanediol, 24 parts of hydrochloric acid, 12 parts of acetone, 12 parts of 3-mercaptopropylsiloxane, 9 parts of n-hexane, 9 parts of dodecafluoroheptyl methacrylate and 9 parts of 2, 2-dimethoxy-phenylacetophenone.
The antibacterial capsule comprises the following raw material components: the seaweed gel comprises, by weight, 15 parts of zinc nitrate, 24 parts of seaweed dry powder, 15 parts of sodium hydroxide, 40 parts of polyvinyl alcohol, 24 parts of ethyl cellulose, 23 parts of dichloromethane, 23 parts of acetone, 15 parts of a freshener and 16 parts of an emulsifier.
The mass ratio of the porous ceramic to the yttrium chloride hexahydrate is 5: 4:3.
The adhesive comprises the following raw material components: by weight, 40 parts of carboxymethyl starch, 50 parts of acrylamide and 25 parts of ammonium persulfate;
example 3
(1) Preparing an adhesive: adding carboxymethyl starch into deionized water, stirring uniformly, gelatinizing at 60 ℃ for 65min, adding acrylamide, stirring, adjusting the pH value to 8.8, adding ammonium persulfate under the nitrogen atmosphere, keeping the temperature and stirring for 7h to obtain an adhesive;
(2) preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 85 ℃, continuously stirring for 3.5h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 15h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 2 hours to obtain a solution A;
c) dissolving ethyl cellulose in dichloromethane and acetone under stirring, adding solution A, freshener and emulsifier, stirring at 1100r/min, adding sodium sulfate, reducing rotation speed to 110r/min, and stirring for 7 hr to obtain antibacterial capsule solution;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 800r/min for 45min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 2h, adding a zinc chloride salt solvent, continuously stirring for 20min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 48 ℃, stirring for reacting for 2.5h, and standing for 24h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 3min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 50min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 5cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(3) preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 50min at 100 ℃, adding porous ceramic, performing ultrasonic dispersion for 6h, taking out and drying, and calcining at 950 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 90 ℃ for 20min, adding modified ceramic, reducing the temperature to 65 ℃, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 80min, adding fiber B, soaking to react for 4h, taking out, washing and drying by using deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 15h, taking out, placing under ultraviolet light to react for 60min, washing by using ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
(4) bonding: and bonding the first non-woven fabric and the second non-woven fabric together by using an adhesive to obtain the biomedical non-woven fabric.
The first non-woven fabric comprises the following raw material components: the antibacterial and heat-insulating material comprises, by weight, 28 parts of antibacterial capsules, 30 parts of gelatin, 27 parts of chitosan, 30 parts of phase-change and temperature-adjusting microcapsules, 60 parts of polyacrylonitrile, 30 parts of acrylamide, 25 parts of polyethylene glycol, 14 parts of 8-hydroxyquinoline copper, 10 parts of acrylic acid, 15 parts of a zinc chloride salt solvent, 14 parts of an oxidant and 10 parts of a reducing agent.
The second non-woven fabric comprises the following raw material components: the modified polyvinyl alcohol modified silicone oil comprises, by weight, 40 parts of modified ceramic, 60 parts of polyvinyl alcohol, 25 parts of pentanediol, 28 parts of hydrochloric acid, 14 parts of acetone, 14 parts of 3-mercaptopropylsiloxane, 10 parts of n-hexane, 10 parts of dodecafluoroheptyl methacrylate and 10 parts of 2, 2-dimethoxy-phenylacetophenone.
The antibacterial capsule comprises the following raw material components: the cooling agent comprises, by weight, 20 parts of zinc nitrate, 28 parts of seaweed dry powder, 20 parts of sodium hydroxide, 50 parts of polyvinyl alcohol, 28 parts of ethyl cellulose, 28 parts of dichloromethane, 27 parts of acetone, 20 parts of a cooling agent and 18 parts of an emulsifier.
The mass ratio of the porous ceramic to the yttrium chloride hexahydrate is 7: 4:3.
The adhesive comprises the following raw material components: 45 parts of carboxymethyl starch, 60 parts of acrylamide and 30 parts of ammonium persulfate;
example 4
Preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 85 ℃, continuously stirring for 3.5h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 15h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 2 hours to obtain a solution A;
c) dissolving ethyl cellulose in dichloromethane and acetone under stirring, adding solution A, freshener and emulsifier, stirring at 1100r/min, adding sodium sulfate, reducing rotation speed to 110r/min, and stirring for 7 hr to obtain antibacterial capsule solution;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 800r/min for 45min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 2h, adding a zinc chloride salt solvent, continuously stirring for 20min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 48 ℃, stirring for reacting for 2.5h, and standing for 24h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 3min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 50min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 5cm sections, and carrying out spunlace to prepare a first non-woven fabric;
example 5
Preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 50min at 100 ℃, adding porous ceramic, performing ultrasonic dispersion for 6h, taking out and drying, and calcining at 950 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 90 ℃ for 20min, adding modified ceramic, reducing the temperature to 65 ℃, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 80min, adding fiber B, soaking to react for 4h, taking out, washing and drying by using deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 15h, taking out, placing under ultraviolet light to react for 60min, washing by using ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
example 6
(1) Preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 85 ℃, continuously stirring for 3.5h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 15h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 2 hours to obtain a solution A;
c) dissolving ethyl cellulose in dichloromethane and acetone under stirring, adding solution A, freshener and emulsifier, stirring at 1100r/min, adding sodium sulfate, reducing rotation speed to 110r/min, and stirring for 7 hr to obtain antibacterial capsule solution;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 800r/min for 45min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 2h, adding a zinc chloride salt solvent, continuously stirring for 20min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 48 ℃, stirring for reacting for 2.5h, and standing for 24h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 3min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 50min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 5cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(2) preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 50min at 100 ℃, adding porous ceramic, performing ultrasonic dispersion for 6h, taking out and drying, and calcining at 950 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 90 ℃ for 20min, adding modified ceramic, reducing the temperature to 65 ℃, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 80min, adding fiber B, soaking to react for 4h, taking out, washing and drying by using deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 15h, taking out, placing under ultraviolet light to react for 60min, washing by using ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
(3) bonding: bonding the first non-woven fabric and the second non-woven fabric together by HY101 glue to obtain the biomedical non-woven fabric.
Example 7
(1) Preparing an adhesive: adding carboxymethyl starch into deionized water, stirring uniformly, gelatinizing at 60 ℃ for 65min, adding acrylamide, stirring, adjusting the pH value to 8.8, adding ammonium persulfate under the nitrogen atmosphere, keeping the temperature and stirring for 7h to obtain an adhesive;
(2) preparing a first nonwoven fabric;
A. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
B. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 800r/min for 45min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 2h, adding a zinc chloride salt solvent, continuously stirring for 20min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 48 ℃, stirring for reacting for 2.5h, and standing for 24h to obtain a shell liquid;
C. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 3min, and taking out to obtain a first fiber;
E. preparing a first nonwoven fabric: cutting the first fiber into 5cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(3) preparing a second non-woven fabric:
A. preparing modified ceramic:
a) preparing porous ceramic;
b) preparing modified ceramic: uniformly mixing sodium hydroxide and yttrium chloride hexahydrate, adding the mixture into deionized water, stirring and dissolving, adding yttrium chloride, heating for 50min at 100 ℃, adding porous ceramic, performing ultrasonic dispersion for 6h, taking out and drying, and calcining at 950 ℃ to obtain modified ceramic;
B. synthesizing a second fiber:
a) stirring polyvinyl alcohol at 90 ℃ for 20min, adding modified ceramic, reducing the temperature to 65 ℃, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 80min, adding fiber B, soaking to react for 4h, taking out, washing and drying by using deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 15h, taking out, placing under ultraviolet light to react for 60min, washing by using ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
(4) bonding: and bonding the first non-woven fabric and the second non-woven fabric together by using an adhesive to obtain the biomedical non-woven fabric.
Example 8
(1) Preparing an adhesive: adding carboxymethyl starch into deionized water, stirring uniformly, gelatinizing at 60 ℃ for 65min, adding acrylamide, stirring, adjusting the pH value to 8.8, adding ammonium persulfate under the nitrogen atmosphere, keeping the temperature and stirring for 7h to obtain an adhesive;
(2) preparing a first nonwoven fabric;
A. preparing an antibacterial capsule:
a) preparing a nano particle A: uniformly mixing zinc nitrate and seaweed dry powder, adding deionized water, stirring for dissolving, raising the temperature to 85 ℃, continuously stirring for 3.5h, cooling to room temperature, adding sodium hydroxide, stirring uniformly, standing for 15h, and performing suction filtration and drying to obtain the nano particles A.
b) Preparation of solution a: adding polyvinyl alcohol into deionized water for dissolving, adding the nano particles A, and performing ultrasonic dispersion for 2 hours to obtain a solution A;
c) dissolving ethyl cellulose in dichloromethane and acetone under stirring, adding solution A, freshener and emulsifier, stirring at 1100r/min, adding sodium sulfate, reducing rotation speed to 110r/min, and stirring for 7 hr to obtain antibacterial capsule solution;
B. preparing a nuclear layer liquid: heating and melting gelatin and chitosan, adding phase-change thermoregulation microcapsule, and stirring uniformly to obtain core layer liquid;
C. preparing a shell layer solution: mixing polyacrylonitrile and acrylamide, heating for melting, adding polyethylene glycol, stirring at a rotating speed of 800r/min for 45min, adding 8-hydroxyquinoline copper and acrylic acid, stirring for reacting for 2h, adding a zinc chloride salt solvent, continuously stirring for 20min, sequentially adding an oxidant and a reducing agent when the temperature is reduced to 48 ℃, stirring for reacting for 2.5h, and standing for 24h to obtain a shell liquid;
D. synthetic fiber A: respectively filling the core layer solution and the shell layer solution into an injector, wrapping the fiber prepared from the shell layer solution onto the fiber prepared from the core layer solution by adopting a coaxial spinning technology, soaking the fiber in alkali liquor for 3min, and taking out to obtain fiber A;
E. etching: adding an initiator and the fiber A into the antibacterial capsule solution, reacting for 50min, taking out and drying to obtain a first fiber;
F. preparing a first nonwoven fabric: cutting the first fiber into 5cm sections, and carrying out spunlace to prepare a first non-woven fabric;
(3) preparing a second non-woven fabric:
synthesizing a second fiber:
a) stirring polyvinyl alcohol at 90 ℃ for 20min, adding common porous ceramic, reducing the temperature to 65 ℃, and performing electrostatic spinning to obtain fiber B;
b) adding hydrochloric acid and acetone into pentanediol, stirring to react for 80min, adding fiber B, soaking to react for 4h, taking out, washing and drying by using deionized water, soaking in a 3-mercaptopropylsiloxane solution, adding n-hexane, carrying out ultrasonic dispersion for 6h, taking out, soaking in a mixed solution of dodecafluoroheptyl methacrylate and 2, 2-dimethoxy-phenylacetophenone to react for 15h, taking out, placing under ultraviolet light to react for 60min, washing by using ethanol, and drying to obtain second fiber;
C. preparing a second non-woven fabric: cutting the second fibers into 5cm small sections, and carrying out spunlace to prepare second non-woven fabrics;
(4) bonding: and bonding the first non-woven fabric and the second non-woven fabric together by using an adhesive to obtain the biomedical non-woven fabric.
The parameters of examples 4-8 are as in example 3; examples 4-8 are comparative experiments in which only the first fibers were prepared in example 4, and the first fibers were made into biomedical nonwoven fabrics by hydroentangling; in example 5, only the second fiber is prepared, and the second fiber is made into the biomedical non-woven fabric through a water jet technology; the first nonwoven fabric and the second nonwoven fabric in example 6 were bonded by YH101 glue to obtain a biomedical nonwoven fabric; the first fiber in example 7 was prepared into biomedical non-woven fabric without adding antibacterial capsules and the remaining parameters were unchanged; in the embodiment 8, the second fiber is directly added with common porous ceramic, and other parameters are not changed to prepare the biomedical non-woven fabric; the biomedical nonwoven fabric samples prepared in examples 1 to 8 were subjected to the following experiments:
and (3) testing antibacterial performance: according to GB/20944.3-2008, evaluation of antibacterial performance of textiles part 3: the test was carried out by the oscillatory method.
Water absorption test: measuring by using a saturated water absorption tester; the water absorption test only tests the first nonwoven side.
And (3) measuring the radiation protection performance: irradiation experiments were performed on biomedical nonwoven fabric samples using an ion implanter, NEC400Kv, usa, with an ion irradiation energy range of 300KeV and an irradiation temperature of 380 ℃.
Hydrophobicity test: and (3) performing a water static contact angle test on the medical non-woven fabric sample by using a contact angle measuring instrument, dropping 2 mu L of liquid on the surface of the film by using a seat dropping method, and reading after 10 s. The rolling angle is measured by an automatic inclination module of a contact angle meter, 5 mu L of water drops are dropped on the surface of the medical non-woven fabric sample, then the horizontal platform is rotated at the rotating speed of 0.5 degree/s, and when the water drops just roll on the surface of the medical non-woven fabric sample, the rotating angle is recorded as the rolling angle of the medical non-woven fabric sample; hydrophobicity test only the second nonwoven side was tested.
Adhesion testing: measured using a LUMiFRac adhesion strength analyzer.
The test results are shown in the following table:
according to the data in the table, only the first fiber is prepared in the example 4, and the biomedical non-woven fabric prepared from the first fiber by the spunlace technology has poor bacteriostatic efficiency of only 52.5 percent, poor hydrophobicity, strong water absorption capacity and no radiation protection capacity; in example 5, only the second fibers are prepared, and the biomedical non-woven fabric prepared from the second fibers by the spunlace technology has insufficient bacteriostasis rate and poor water absorption capacity, but has excellent hydrophobic capacity and radiation protection capacity; compared with the biomedical non-woven fabric obtained by bonding the first non-woven fabric and the second non-woven fabric through YH101 glue in example 6, the test results are general, the adhesion is insufficient, and the hydrophobic property and the radiation protection property are excellent; in the embodiment 7, the first fiber is not added with the antibacterial capsule, and other parameters are not changed, so that the prepared biomedical non-woven fabric has insufficient antibacterial rate, and other performance performances are ideal; the second fiber in the embodiment 8 is directly added with the common porous ceramic, and other parameters are not changed, so that the prepared biomedical non-woven fabric has better adhesion performance, and other performances have larger differences compared with the performances in the embodiments 1 to 3;
from the above data and experiments, we can conclude that: 1. the common non-woven fabric has insufficient bacteriostatic ability and certain water absorption capacity, but the common non-woven fabric has general water absorption capacity, cannot meet the working requirements of medical personnel and does not have radiation protection capability, and because the common glue is used, the adhesive strength is insufficient, and the fabric is easy to have a layering phenomenon; the invention is mainly divided into two layers, one layer is a first non-woven fabric with super-hydrophilic and antibacterial properties, the other layer is a second non-woven fabric with super-hydrophobic, radiation-proof and antibacterial functions, the two non-woven fabrics are bonded by a special adhesive, the prepared biomedical antibacterial non-woven fabric is capable of effectively absorbing sweat by the first non-woven fabric tightly attached to the skin, regulating and controlling the temperature in the protective clothing, releasing antibacterial nano particles and a freshener for a long time, refreshing the mind and improving the wearing comfort of medical personnel, the other layer of second non-woven fabric has stronger antibacterial performance and radiation-proof capability due to the existence of modified ceramic, the second non-woven fabric prepared by mixing the modified ceramic and the super-hydrophobic spinning solution has stronger hydrophobic capability, and can effectively prevent stains and blood from attaching; by utilizing the synergistic effect of the first non-woven fabric, the second non-woven fabric and the adhesive, the prepared biomedical non-woven fabric has the capabilities of phase change temperature regulation, moisture absorption, antibiosis, blood repellency and radiation resistance, can effectively resist the invasion of microorganisms and pathogens while improving the wearing comfort of medical personnel, and has practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.