CN114657707A - Preparation method of waterproof, moisture-permeable and antibacterial nanofiber membrane - Google Patents
Preparation method of waterproof, moisture-permeable and antibacterial nanofiber membrane Download PDFInfo
- Publication number
- CN114657707A CN114657707A CN202210543918.5A CN202210543918A CN114657707A CN 114657707 A CN114657707 A CN 114657707A CN 202210543918 A CN202210543918 A CN 202210543918A CN 114657707 A CN114657707 A CN 114657707A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- nanofiber membrane
- permeable
- waterproof
- antibacterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 239000002121 nanofiber Substances 0.000 title claims abstract description 73
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 52
- 239000004814 polyurethane Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 238000009987 spinning Methods 0.000 claims abstract description 39
- 229920001661 Chitosan Polymers 0.000 claims abstract description 32
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000004890 Hydrophobing Agent Substances 0.000 description 5
- -1 perfluoro Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006306 polyurethane fiber Polymers 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- 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
- D04H1/4326—Condensation or reaction polymers
- D04H1/4358—Polyurethanes
-
- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of a waterproof, moisture permeable and antibacterial nanofiber membrane, which comprises the following steps: step one, preparing silane coupling agent modified graphene oxide powder; step two, preparing carboxymethyl chitosan modified graphene oxide powder; and step three, preparing the waterproof, moisture permeable and antibacterial nanofiber membrane. The waterproof moisture-permeable antibacterial nanofiber membrane prepared in the invention not only improves the moisture permeability of the polyurethane nanofiber membrane, but also greatly improves the waterproof performance, antibacterial performance and mechanical performance. According to the invention, carboxymethyl chitosan is used as an antibacterial agent, carboxymethyl chitosan is used for modifying graphene oxide, and the modified graphene oxide is directly added into spinning solution for electrostatic spinning to prepare the nanofiber membrane. Not only the nanofiber membrane has antibacterial performance, but also the nanofiber membrane is harmless to human bodies. The nanofiber membrane prepared by the method still has excellent antibacterial performance after being washed for many times.
Description
Technical Field
The invention belongs to the field of electrostatic spinning functional materials, particularly relates to a preparation method of a waterproof, moisture-permeable and antibacterial nanofiber membrane, and particularly relates to a modified graphene oxide polyurethane waterproof, moisture-permeable and antibacterial nanofiber membrane and a preparation method thereof.
Background
The polyurethane material has the advantages of excellent elasticity, easiness in compounding and the like, and the polyurethane nanofiber membrane with the diameter of 50-500 nm is prepared through an electrostatic spinning method, and the prepared nanofiber membrane has porosity, good mechanical property and good moisture permeability. However, the waterproof performance of the polyurethane nanofiber membrane is poor, so that the improvement of the moisture permeability, the waterproof performance and other wearability of the polyurethane fiber membrane is a main development direction.
At present, researchers add water repellent fluorine-containing polyurethane into a polyurethane spinning solution or introduce fluorine groups into a polyurethane structure, so that excellent low surface performance, water resistance, stain resistance and the like can be endowed to a polyurethane nanofiber membrane, and a patent 202010025937.X also provides a waterproof moisture-permeable composite fabric containing fluorinated graphene and a preparation method thereof. However, research shows that the perfluoro alkyl acid generated by the degradation of perfluoro or polyfluoro compounds has potential toxicity and the capability of long-distance migration, and has serious influence on the health of people and the environmental safety. At present, research on fluorine-free hydrophobing agents is more and more extensive, and the organosilicon hydrophobing agents are the most used fluorine-free hydrophobing agents at present and have inorganic structures and organic groups, so that the organosilicon hydrophobing agents have the characteristics of inorganic matters and organic matters. The graphene oxide improves the mechanical property of the polyurethane nanofiber membrane, and the graphene oxide is modified by the silane coupling agent and then added into the electrostatic spinning solution to prepare the waterproof moisture-permeable nanofiber membrane.
The application of the waterproof moisture permeable polyurethane nanofiber membrane is very wide, and the polyurethane nanofiber membrane can be applied to the medical health industry and used for manufacturing medical protective surgical gowns, surgical towels and pull curtains in wards,The materials such as bedsheets, quilt covers, gloves, masks, gauze for wrapping wounds and the like, and the used polyurethane nanofiber membrane needs to have certain antibacterial performance. Patent 202010025938.4 discloses an electrospun double-layer long-acting antibacterial medical dressing. The outer layer is sodium polyacrylate and polyvinyl alcohol blended water-absorbent fiber added with an antibacterial agent, the inner layer is polyurethane hydrophilic fiber added with a small amount of the antibacterial agent, and the two layers of nanofiber membranes are bonded by hot melt adhesive to prepare the double-layer dressing with good air permeability, moisture permeability, water absorption performance and antibacterial performance. However, the method needs to prepare a double-layer dressing and then use hot melt adhesive for bonding, and the preparation process is complex. Patent 201510934499.8 discloses a method for preparing a superhydrophobic or superhydrophilic antibacterial nanofiber membrane by immersing a nanofiber membrane prepared by electrospinning in a suspension mixture of quaternary ammonium salt and nanoparticles. The patent 201911331213.1 also discloses that the prepared composite fiber membrane is soaked in an environment-friendly antibacterial finishing agent solution, and is cured after heat treatment, so as to finally prepare the composite electrostatic spinning waterproof moisture-permeable membrane with antibacterial property. The antibacterial nanofiber membrane prepared by the soaking method, the coating method, the spraying method and other methods has the advantages of wide applicable fiber fabric range, lower processing cost and the like, but the prepared antibacterial fiber membrane has poorer water washing resistance, and the antibacterial performance of the nanofiber membrane is greatly reduced after multiple times of washing. And the antibacterial agent is directly added into the spinning solution, and the nanofiber membrane prepared by electrostatic spinning has high antibacterial rate and lasting antibacterial effect. Patent 201610039771.0 AgNO is added into spinning solution3And (3) preparing an antibacterial waterborne polyurethane nanofiber membrane by using an aqueous solution. However, the nano silver has cytotoxicity with different degrees and has different degrees of harm to various organs of a human body. According to the preparation method, carboxymethyl chitosan is used as an antibacterial agent and is used for modifying graphene oxide, so that the prepared nanofiber membrane has antibacterial performance and mechanical performance.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects of the prior art and provides a preparation method of a waterproof moisture-permeable antibacterial nanofiber membrane, the method is simple in process, and the prepared polyurethane nanofiber membrane has the waterproof moisture-permeable performance, the antibacterial performance and the mechanical performance and is green and environment-friendly and harmless to human bodies and the environment.
The technical scheme is as follows: a preparation method of a waterproof, moisture permeable and antibacterial nanofiber membrane comprises the following steps:
step one, preparing silane coupling agent modified graphene oxide powder: preparing small pieces of graphene oxide by an improved Hummers method, and preparing 1-5 mg/mL graphene oxide aqueous dispersion; adding a silane coupling agent into the graphene oxide aqueous dispersion for reaction; after the reaction is finished, washing the reaction product for many times by using deionized water until colorless transparent residual liquid is obtained; finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain silane coupling agent modified graphene oxide powder;
step two, preparing carboxymethyl chitosan modified graphene oxide powder: preparing small pieces of graphene oxide by an improved Hummers method, and preparing 1-5 mg/mL graphene oxide aqueous dispersion; respectively adding carboxymethyl chitosan and hydrazine hydrate into the graphene oxide aqueous dispersion for reaction; after the reaction is finished, washing the reaction product for many times by using deionized water until colorless transparent residual liquid is obtained; finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain carboxymethyl chitosan modified graphene oxide powder;
step three, preparing the waterproof, moisture permeable and antibacterial nanofiber membrane: sequentially adding silane coupling agent modified graphene oxide powder and carboxymethyl chitosan modified graphene oxide powder into a mixed solution of tetrahydrofuran and N, N-dimethylformamide, and performing ultrasonic treatment until the mixed solution is uniformly dispersed; respectively adding lithium chloride and polyurethane particles into the mixed solution, and stirring to obtain uniform polyurethane spinning solution; finally, the waterproof, moisture permeable and antibacterial polyurethane nanofiber membrane is prepared by an electrostatic spinning method.
Further, in the first step and the second step, the improved Hummers method is that under the ice bath condition, 6g of graphite is added into a beaker containing 500mL of concentrated sulfuric acid, 30g of potassium permanganate is slowly added under magnetic stirring, and after stirring in an ice bath for 6 hours, stirring is continued for 1 day at normal temperature; then, slowly adding 500mL of deionized water under the ice bath condition, stirring for 1 day, and then adding 50mL of hydrogen peroxide; when the reaction solution turned bright yellow, 50mL of 5% hydrochloric acid solution was added, and finally, the mixture was washed with deionized water several times until the pH of the suspension was neutral, and then freeze-dried.
Further, in the first step and the second step, the diameter size of the small pieces of oxidized graphene is less than 5 μm.
Further, in the first step, the silane coupling agent is one or more of isocyanatopropyl triethoxysilane, vinyl triethoxysilane, gamma-glycidyl ether oxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane; the mass ratio of the silane coupling agent to the graphene oxide is 1: 8 to 11.
Further, in the first step, the reaction condition is that the temperature is 70-90 ℃ and the time is 5-24 hours.
Further, in the second step, the carboxylation degree of the carboxymethyl chitosan is more than or equal to 80 percent; the mass ratio of the carboxymethyl chitosan to the graphene oxide to the hydrazine hydrate is (209.42-218.57): (138.99-145.71): (0.96-1.04).
Further, in the second step, the reaction condition is that the temperature is 80-100 ℃ and the time is 1.5-4 h.
Further, in the third step, the mass fraction of the silane coupling agent modified graphene oxide powder in the polyurethane spinning solution is 0.01-1%, the mass fraction of the carboxymethyl chitosan modified graphene oxide powder is 0.01-1%, the mass fraction of the lithium chloride is 0.001-0.01%, and the mass fraction of the polyurethane particles is 14-24%; the mass ratio of tetrahydrofuran to N, N-dimethylformamide is 2-4: 1.
further, in the third step, the stirring condition is that the temperature is 30-60 ℃ and the time is 1-10 hours.
Furthermore, in the third step, the parameters of the waterproof, moisture permeable and antibacterial polyurethane nanofiber membrane electrospinning are spinning voltage of 15-25 KV, the distance between a spray head and a receiving roller is 12-19 cm, the injection speed is 2-6 mL/h, the rotating speed of a roller is 100-150 rpm, the operating speed of a sliding table is 100-200 mm/min, the spinning temperature is 24-26 ℃, and the spinning humidity is 30-50%.
Has the advantages that: the specific advantages of the invention are as follows:
(1) the waterproof moisture-permeable antibacterial nanofiber membrane prepared by the method not only improves the moisture permeability of the polyurethane nanofiber membrane, but also greatly improves the waterproof performance, antibacterial performance and mechanical performance of the polyurethane nanofiber membrane.
(2) Compared with the existing patents, the method utilizes the fluorine-free silane coupling agent to modify the graphene oxide, thereby not only avoiding the use of fluorine hydrophobing agents, but also improving the waterproof, moisture permeable and mechanical properties of the nanofiber membrane.
(3) According to the invention, carboxymethyl chitosan is used as an antibacterial agent, carboxymethyl chitosan is used for modifying graphene oxide, and the graphene oxide is directly added into spinning solution for electrostatic spinning to prepare the nanofiber membrane. Not only the nanofiber membrane has antibacterial performance, but also the nanofiber membrane does not harm human bodies. The nanofiber membrane prepared by the method still has excellent antibacterial performance after being washed for many times.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Examples
Example 1
Preparing gamma-glycidyl ether oxypropyltrimethoxysilane modified graphene oxide powder: the platelet-oxidized graphene is prepared by a modified Hummers method, and a 1mg/mL aqueous graphene oxide dispersion is prepared. 10mL of gamma-glycidoxypropyltrimethoxysilane was added to 100mL of the aqueous graphene oxide dispersion and reacted at 90 ℃ for 12 hours. After the reaction is finished, washing the reaction product for many times by deionized water until colorless transparent residual liquid is obtained. Finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain gamma-glycidyl ether oxypropyltrimethoxysilane modified graphene oxide powder;
preparing carboxymethyl chitosan modified graphene oxide powder: the platelet-oxidized graphene is prepared by a modified Hummers method, and a 1mg/mL aqueous graphene oxide dispersion is prepared. 0.15g of carboxymethyl chitosan and 35 muL of hydrazine hydrate are respectively added into 100mL of graphene oxide aqueous dispersion and reacted for 2h at 90 ℃. After the reaction is finished, washing the reaction product for many times by deionized water until colorless transparent residual liquid is obtained. Finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain carboxymethyl chitosan modified graphene oxide powder;
preparing a waterproof, moisture permeable and antibacterial nanofiber membrane: 0.06g of gamma-glycidyl ether oxypropyltrimethoxysilane modified graphene oxide powder and 0.01g of carboxymethyl chitosan modified graphene oxide powder are sequentially added into a mixed solution of 24.6g of tetrahydrofuran and 8.2g N, N-dimethylformamide, and ultrasonic treatment is carried out until the mixed solution is uniformly dispersed. Then, 0.004g of lithium chloride and 5.6g of polyurethane particles were added to the mixed solution, respectively, and stirred at 50 ℃ for 6 hours to obtain a uniform polyurethane spinning solution. Finally, the waterproof moisture-permeable antibacterial polyurethane nanofiber membrane is prepared by an electrostatic spinning method under the conditions that the spinning voltage is 20KV, the distance between a spray head and a receiving roller is 15cm, the injection speed is 2.5mL/h, the rotating speed of a roller is 100rpm, the running speed of a sliding table is 100mm/min, the spinning temperature is 25 ℃, and the spinning humidity is 40%.
Example 2
Preparing gamma-glycidyl ether oxypropyltrimethoxysilane modified graphene oxide powder: the platelet-oxidized graphene is prepared by a modified Hummers method, and a 1mg/mL aqueous graphene oxide dispersion is prepared. 10mL of gamma-glycidoxypropyltrimethoxysilane was added to 100mL of the aqueous graphene oxide dispersion and reacted at 90 ℃ for 12 hours. After the reaction is finished, washing the reaction product for many times by deionized water until colorless transparent residual liquid is obtained. Finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain gamma-glycidyl ether oxypropyltrimethoxysilane modified graphene oxide powder;
preparing carboxymethyl chitosan modified graphene oxide powder: the platelet-oxidized graphene is prepared by a modified Hummers method, and a 1mg/mL aqueous graphene oxide dispersion is prepared. 0.15g of carboxymethyl chitosan and 35 muL of hydrazine hydrate are respectively added into 100mL of graphene oxide aqueous dispersion and reacted for 2h at 90 ℃. After the reaction is finished, washing the reaction product for many times by deionized water until colorless transparent residual liquid is obtained. Finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain carboxymethyl chitosan modified graphene oxide powder;
preparing a waterproof, moisture permeable and antibacterial nanofiber membrane: 0.12g of gamma-glycidyl ether oxypropyltrimethoxysilane modified graphene oxide powder and 0.03g of carboxymethyl chitosan modified graphene oxide powder are sequentially added into a mixed solution of 24.6g of tetrahydrofuran and 8.2g N, N-dimethylformamide, and ultrasonic treatment is carried out until the mixed solution is uniformly dispersed. Then, 0.004g of lithium chloride and 5.6g of polyurethane particles were added to the mixed solution, respectively, and stirred at 55 ℃ for 4 hours to obtain a uniform polyurethane spinning solution. Finally, the waterproof moisture-permeable antibacterial polyurethane nanofiber membrane is prepared by an electrostatic spinning method under the conditions that the spinning voltage is 20KV, the distance between a spray head and a receiving roller is 15cm, the injection speed is 2.5mL/h, the rotating speed of a roller is 100rpm, the running speed of a sliding table is 100mm/min, the spinning temperature is 25 ℃, and the spinning humidity is 40%.
Example 3
Preparing gamma-aminopropyltriethoxysilane modified graphene oxide powder: the platelet-oxidized graphene is prepared by a modified Hummers method, and a 1mg/mL aqueous graphene oxide dispersion is prepared. 10mL of gamma-aminopropyltriethoxysilane was added to 100mL of aqueous graphene oxide dispersion and reacted at 95 ℃ for 10 h. After the reaction is finished, washing the reaction product for many times by deionized water until colorless transparent residual liquid is obtained. Finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain gamma-aminopropyl triethoxysilane modified graphene oxide powder;
preparing carboxymethyl chitosan modified graphene oxide powder: the platelet-oxidized graphene is prepared by a modified Hummers method, and a 1mg/mL aqueous graphene oxide dispersion is prepared. 0.15g of carboxymethyl chitosan and 35 muL of hydrazine hydrate are respectively added into 100mL of graphene oxide aqueous dispersion and reacted for 2h at 90 ℃. After the reaction is finished, washing the reaction product for many times by deionized water until colorless transparent residual liquid is obtained. Finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain carboxymethyl chitosan modified graphene oxide powder;
preparing a waterproof, moisture permeable and antibacterial nanofiber membrane: 0.12g of gamma-aminopropyltriethoxysilane-modified graphene oxide powder and 0.03g of carboxymethyl chitosan-modified graphene oxide powder are sequentially added into a mixed solution of 24.6g of tetrahydrofuran and 8.2g N, N-dimethylformamide, and ultrasonic treatment is carried out until the mixed solution is uniformly dispersed. Then, 0.004g of lithium chloride and 5.6g of polyurethane particles were added to the mixed solution, respectively, and stirred at 50 ℃ for 6 hours to obtain a uniform polyurethane spinning solution. Finally, the waterproof moisture-permeable antibacterial polyurethane nanofiber membrane is prepared by an electrostatic spinning method under the conditions that the spinning voltage is 20KV, the distance between a spray head and a receiving roller is 15cm, the injection speed is 2.5mL/h, the rotating speed of a roller is 100rpm, the running speed of a sliding table is 100mm/min, the spinning temperature is 25 ℃, and the spinning humidity is 40%.
Comparative example 1
Preparing a waterproof moisture-permeable polyurethane fiber film: 0.004g of lithium chloride and 5.6g of polyurethane particles were added to a mixed solution of 24.6g of tetrahydrofuran and 8.2g N, N-dimethylformamide, respectively, and stirred at 50 ℃ for 6 hours to obtain a uniform polyurethane spinning solution. And then preparing the waterproof moisture-permeable polyurethane nanofiber membrane by an electrostatic spinning method under the conditions that the spinning voltage is 20KV, the distance between a spray head and a receiving roller is 15cm, the injection speed is 2.5mL/h, the rotating speed of a roller is 100rpm, the running speed of a sliding table is 100mm/min, the spinning temperature is 25 ℃, and the spinning humidity is 40%.
Comparative example 2
Preparing a polyurethane fiber membrane: 5.6g of polyurethane particles were added to a mixed solution of 24.6g of tetrahydrofuran and 8.2g N, N-dimethylformamide and stirred at 50 ℃ for 6 hours to obtain a uniform polyurethane spinning solution. And then preparing the polyurethane nanofiber membrane by an electrostatic spinning method under the conditions that the spinning voltage is 20KV, the distance between a spray head and a receiving roller is 15cm, the injection speed is 2.5mL/h, the rotating speed of a roller is 100rpm, the running speed of a sliding table is 100mm/min, the spinning temperature is 25 ℃, and the spinning humidity is 40%.
The waterproof moisture-permeable antibacterial nanofiber membrane is subjected to index test as follows: the moisture permeability test refers to GB/T12704-2009 part 1 of textile moisture permeability test method: wet absorption method.
The waterproof performance test refers to GB/T4744-2013 detection and evaluation of textile waterproof performance.
The mechanical property test refers to GB/T3923.1-2013 part 1 of tensile property of textile fabric: bar test for determination of breaking strength and breaking elongation.
The antibacterial performance test is referred to the AATCC100-2012 standard. Staphylococcus aureus was used as a gram-positive bacterium, and Escherichia coli was used as a gram-negative bacterium.
TABLE 1 moisture-permeable and antibacterial nanofiber membrane moisture permeability, water resistance and mechanical property test
TABLE 2 antibacterial Performance test of waterproof, moisture permeable, antibacterial nanofiber films
Lithium chloride is added into the polyurethane spinning solution, so that the conductivity of the solution can be improved, a more stable spinning diameter is obtained, and the problem of poor waterproof and moisture-permeable performance of the polyurethane nanofiber membrane is solved to a certain extent. It is seen from table 1 that the moisture permeability and water pressure resistance of the polyurethane nanofiber membrane can be improved to a certain extent by adding lithium chloride into the spinning solution, but the mechanical properties of the fiber membrane are reduced by adding lithium chloride. And the silane coupling agent is added into the spinning solution to modify the graphene oxide, so that the prepared waterproof moisture-permeable polyurethane nanofiber membrane has excellent waterproof moisture-permeable performance, and the mechanical property of the polyurethane nanofiber membrane is greatly improved. From table 2, the addition of carboxymethyl chitosan modified graphene oxide greatly improves the antibacterial performance of the polyurethane nanofiber membrane, and the waterproof moisture permeable polyurethane nanofiber membrane still has good antibacterial performance even after 10 times of washing.
Claims (10)
1. A preparation method of a waterproof, moisture permeable and antibacterial nanofiber membrane is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing silane coupling agent modified graphene oxide powder: preparing small pieces of graphene oxide by an improved Hummers method, and preparing 1-5 mg/mL graphene oxide aqueous dispersion; adding a silane coupling agent into the graphene oxide aqueous dispersion for reaction; after the reaction is finished, washing the reaction product for many times by using deionized water until colorless transparent residual liquid is obtained; finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain silane coupling agent modified graphene oxide powder;
step two, preparing carboxymethyl chitosan modified graphene oxide powder: preparing small pieces of graphene oxide by an improved Hummers method, and preparing 1-5 mg/mL graphene oxide aqueous dispersion; respectively adding carboxymethyl chitosan and hydrazine hydrate into the graphene oxide aqueous dispersion for reaction; after the reaction is finished, washing the reaction product for many times by using deionized water until colorless transparent residual liquid is obtained; finally, ultrasonically dispersing the product uniformly, and carrying out vacuum freeze drying to obtain carboxymethyl chitosan modified graphene oxide powder;
step three, preparing the waterproof, moisture permeable and antibacterial nanofiber membrane: sequentially adding silane coupling agent modified graphene oxide powder and carboxymethyl chitosan modified graphene oxide powder into a mixed solution of tetrahydrofuran and N, N-dimethylformamide, and carrying out ultrasonic treatment until the mixed solution is uniformly dispersed; respectively adding lithium chloride and polyurethane particles into the mixed solution, and stirring to obtain uniform polyurethane spinning solution; finally, the waterproof, moisture permeable and antibacterial polyurethane nanofiber membrane is prepared by an electrostatic spinning method.
2. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the first step and the second step, the improved Hummers method is that under the ice bath condition, 6g of graphite is added into a beaker containing 500mL of concentrated sulfuric acid, 30g of potassium permanganate is slowly added under magnetic stirring, and after stirring in an ice bath for 6 hours, stirring is continued for 1 day at normal temperature; then, slowly adding 500mL of deionized water under the ice bath condition, stirring for 1 day, and then adding 50mL of hydrogen peroxide; when the reaction solution turned bright yellow, 50mL of 5% hydrochloric acid solution was added, and finally, the mixture was washed with deionized water several times until the pH of the suspension was neutral, and then freeze-dried.
3. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the first step and the second step, the diameter size of the small pieces of oxidized graphene is less than 5 mu m.
4. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the first step, the silane coupling agent is one or a combination of more of isocyanatopropyl triethoxysilane, vinyl triethoxysilane, gamma-glycidyl ether oxypropyl trimethoxysilane and gamma-aminopropyl triethoxysilane; the mass ratio of the silane coupling agent to the graphene oxide is 1: 8 to 11.
5. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the first step, the reaction condition is that the temperature is 70-90 ℃ and the time is 5-24 h.
6. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the second step, the carboxylation degree of the carboxymethyl chitosan is more than or equal to 80 percent; the mass ratio of the carboxymethyl chitosan to the graphene oxide to the hydrazine hydrate is (209.42-218.57): (138.99-145.71): (0.96-1.04).
7. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the second step, the reaction condition is that the temperature is 80-100 ℃ and the time is 1.5-4 h.
8. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the third step, the mass fraction of the silane coupling agent modified graphene oxide powder in the polyurethane spinning solution is 0.01-1%, the mass fraction of the carboxymethyl chitosan modified graphene oxide powder is 0.01-1%, the mass fraction of the lithium chloride is 0.001-0.01%, and the mass fraction of the polyurethane particles is 14-24%; the mass ratio of tetrahydrofuran to N, N-dimethylformamide is 2-4: 1.
9. the preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the third step, the stirring is carried out at the temperature of 30-60 ℃ for 1-10 h.
10. The preparation method of the waterproof moisture-permeable antibacterial nanofiber membrane as claimed in claim 1, characterized in that: in the third step, parameters of the waterproof moisture-permeable antibacterial polyurethane nanofiber membrane electrospinning are spinning voltage of 15-25 KV, the distance from a spray head to a receiving roller is 12-19 cm, the injection speed is 2-6 mL/h, the rotating speed of a roller is 100-150 rpm, the operating speed of a sliding table is 100-200 mm/min, the spinning temperature is 24-26 ℃, and the spinning humidity is 30-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210543918.5A CN114657707A (en) | 2022-05-19 | 2022-05-19 | Preparation method of waterproof, moisture-permeable and antibacterial nanofiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210543918.5A CN114657707A (en) | 2022-05-19 | 2022-05-19 | Preparation method of waterproof, moisture-permeable and antibacterial nanofiber membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114657707A true CN114657707A (en) | 2022-06-24 |
Family
ID=82037056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210543918.5A Pending CN114657707A (en) | 2022-05-19 | 2022-05-19 | Preparation method of waterproof, moisture-permeable and antibacterial nanofiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114657707A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323622A (en) * | 2022-08-11 | 2022-11-11 | 广东汇齐新材料有限公司 | Waterproof moisture-permeable nanofiber membrane and preparation method thereof |
| CN115874355A (en) * | 2022-12-07 | 2023-03-31 | 山东大学 | Fluoride-free waterproof moisture permeable nanofiber membrane and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864837A (en) * | 2018-06-11 | 2018-11-23 | 安徽大学 | Double-bond modified graphene/polyvinylidene chloride heavy-duty anticorrosive coating and preparation method thereof |
| CN109233253A (en) * | 2018-09-20 | 2019-01-18 | 徐冬 | A kind of preparation method of waterproof ventilation polyurethane film |
| CN109576906A (en) * | 2018-12-25 | 2019-04-05 | 江苏国源环境科技有限公司 | Air dewetting and the dual-purpose electrostatic spinning nano fiber film and preparation method thereof of filtering |
| CN109666149A (en) * | 2018-11-20 | 2019-04-23 | 兴业皮革科技股份有限公司 | A kind of preparation method of the graphene-based polysiloxanes of silicon oxygen six-membered ring structure |
| CN112011147A (en) * | 2020-08-11 | 2020-12-01 | 瞿雨捷 | Long glass fiber reinforced flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN112063263A (en) * | 2020-07-31 | 2020-12-11 | 嵊州市鉴亭新材料科技有限公司 | Super-hydrophobic rGO-Ag-modified epoxy resin anticorrosive paint and preparation method thereof |
| CN112266492A (en) * | 2020-11-21 | 2021-01-26 | 蚌埠市维光塑胶制品有限公司 | Preparation method of hydrophobic film with low water absorption |
| CN113831825A (en) * | 2021-08-23 | 2021-12-24 | 武汉科技大学 | Self-repairing waterborne polyurethane anticorrosive paint and preparation method thereof |
| CN114232122A (en) * | 2021-04-13 | 2022-03-25 | 海宁恒爱新材料有限公司 | Preparation method of polyacrylonitrile composite fiber membrane with antibacterial property |
| CN114232213A (en) * | 2021-05-06 | 2022-03-25 | 杭州佳杭新材料科技有限公司 | Preparation method of modified polyacrylonitrile fiber membrane with antibacterial property |
-
2022
- 2022-05-19 CN CN202210543918.5A patent/CN114657707A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864837A (en) * | 2018-06-11 | 2018-11-23 | 安徽大学 | Double-bond modified graphene/polyvinylidene chloride heavy-duty anticorrosive coating and preparation method thereof |
| CN109233253A (en) * | 2018-09-20 | 2019-01-18 | 徐冬 | A kind of preparation method of waterproof ventilation polyurethane film |
| CN109666149A (en) * | 2018-11-20 | 2019-04-23 | 兴业皮革科技股份有限公司 | A kind of preparation method of the graphene-based polysiloxanes of silicon oxygen six-membered ring structure |
| CN109576906A (en) * | 2018-12-25 | 2019-04-05 | 江苏国源环境科技有限公司 | Air dewetting and the dual-purpose electrostatic spinning nano fiber film and preparation method thereof of filtering |
| CN112063263A (en) * | 2020-07-31 | 2020-12-11 | 嵊州市鉴亭新材料科技有限公司 | Super-hydrophobic rGO-Ag-modified epoxy resin anticorrosive paint and preparation method thereof |
| CN112011147A (en) * | 2020-08-11 | 2020-12-01 | 瞿雨捷 | Long glass fiber reinforced flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN112266492A (en) * | 2020-11-21 | 2021-01-26 | 蚌埠市维光塑胶制品有限公司 | Preparation method of hydrophobic film with low water absorption |
| CN114232122A (en) * | 2021-04-13 | 2022-03-25 | 海宁恒爱新材料有限公司 | Preparation method of polyacrylonitrile composite fiber membrane with antibacterial property |
| CN114232213A (en) * | 2021-05-06 | 2022-03-25 | 杭州佳杭新材料科技有限公司 | Preparation method of modified polyacrylonitrile fiber membrane with antibacterial property |
| CN113831825A (en) * | 2021-08-23 | 2021-12-24 | 武汉科技大学 | Self-repairing waterborne polyurethane anticorrosive paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 史飞龙: "多组分改性氧化石墨烯的制备及应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323622A (en) * | 2022-08-11 | 2022-11-11 | 广东汇齐新材料有限公司 | Waterproof moisture-permeable nanofiber membrane and preparation method thereof |
| CN115874355A (en) * | 2022-12-07 | 2023-03-31 | 山东大学 | Fluoride-free waterproof moisture permeable nanofiber membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114657707A (en) | Preparation method of waterproof, moisture-permeable and antibacterial nanofiber membrane | |
| CN111705509B (en) | Graphene-based lasting antibacterial composite garment fabric | |
| CN111379161A (en) | Preparation method of silver ion antibacterial non-woven fabric | |
| CN107022895B (en) | Fabric with flame-retardant coating and preparation method thereof | |
| CN114086394B (en) | Treatment process of non-woven fabric for mask | |
| CN112900089A (en) | Waterproof fiber knitted fabric and preparation method thereof | |
| CN112481760B (en) | Antibacterial and antifouling organic cotton and kapok blended yarn and preparation method thereof | |
| CN101914849B (en) | Aluminum hydroxide sol-coated high-temperature-resistant fiber fabric and preparation method thereof | |
| CN112941910A (en) | Antibacterial fiber blended fabric and preparation method thereof | |
| Taheri et al. | A Cleaner affordable method for production of bactericidal textile substrates by in situ deposition of ZnO/Ag nanoparticles | |
| Arif et al. | Synthesis of nanomaterials and their applications in textile industry | |
| CN1299576C (en) | Slicon dioxide-cladding tourmaline and titanium dioxide particle composite antibacterial material, its preparation and application | |
| CN113981619A (en) | Nano antibacterial non-woven fabric filter material and preparation method thereof | |
| CN114654841B (en) | Preparation method of polyester-based waterproof moisture-permeable flame-retardant composite material | |
| CN114318578A (en) | Antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber and preparation method thereof | |
| CN116254699B (en) | Anti-bacterial textile based on difunctional boron nitride and preparation method thereof | |
| CN116536791A (en) | Modified graphene polylactic acid antibacterial fiber and preparation method and application thereof | |
| CN116590918A (en) | Preparation method of antistatic wool fiber | |
| CN107412882B (en) | Preparation method of attached flexible artificial skin receptor | |
| CN115874458A (en) | Heat-insulation curtain fabric and preparation method thereof | |
| CN113417026A (en) | Graphene high-thermal-insulation fiber and preparation method thereof | |
| CN106917266B (en) | antibacterial natural silk fiber product and preparation method thereof | |
| CN109281160B (en) | Preparation method of silver nanowire modified temperature-sensitive variable resistance fiber with sterilization effect | |
| CN114232344B (en) | PM2.5 filtering SPAP film with antibacterial and antifouling functions and preparation method thereof | |
| CN117818175B (en) | Antibacterial and anti-mite composite fabric and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220624 |
|
| RJ01 | Rejection of invention patent application after publication |