CN110409010A - Nanofiber with nano-protrusion structure on the surface and preparation method thereof - Google Patents

Abstract

The invention discloses a nanofiber with a nano-protrusion structure on the surface and a preparation method thereof. Specifically, thermoplastic polymers and nanoparticles are melt-blended to prepare nanoparticle/thermoplastic polymer composites, and then the resulting composites are blended with cellulose acetate butyrate in proportion to melt spinning, and the cellulose acetate butyrate is removed by solvent extraction. , preparing nanoparticle/thermoplastic polymer composite nanofibers, and then soaking in a solvent to obtain nanofibers with nano-protruding structures on the surface. The present invention regulates the microstructure of the nanofiber by controlling the type of loaded nanoparticle, controlling the soaking temperature, time, solvent type, etc., and then regulates the performance of the nanofiber. The nanofibers with nano-protrusion structures on the surface prepared by the present invention can control the shape and size of the nano-protrusions, can realize the loading of nanoparticles with different properties, and have potential applications in the fields of filtration, adsorption, catalysis, antibacterial and the like.

Description

Nanofiber with nano-protrusion structure on the surface and preparation method thereof

technical field

The invention relates to the field of nanomaterials, in particular to a nanofiber with a nanoprotrusion structure on the surface and a preparation method thereof.

Background technique

Nanofibers have the characteristics of large aspect ratio, large specific surface area, and easy film formation, and are widely used in medicine, food, environment, energy and other fields. The nanofiber membrane material has high porosity and small pore size, which increases the probability of blocking and adsorbing small particles in the medium, thereby improving the filtration efficiency. At the same time, as a microfiltration material, nanofiber material allows macromolecules and dissolved solids to pass through, but intercepts suspended solids, bacteria, and large molecular weight colloids, so it has a better barrier effect on bacteria and other microorganisms. At present, the diameter of nanofibers can reach tens or even tens of nanometers, but due to the single fiber structure, it cannot meet the application requirements of high-efficiency filtration, adsorption, catalysis, and antibacterial. Nanoparticles have small size effect, surface effect, interface effect and quantum tunneling effect, etc. These effects can lead to abnormal adsorption ability, chemical reaction ability, dispersion and agglomeration ability, solubility in different media, thermal properties, photocatalysis performance and surface activity. Therefore, it is a current research hotspot to prepare functional nanofibers by combining nanoparticles as functional carriers with nanofibers.

In the invention patent with the application number CN201410193018.8, a high-adsorption nanofiber composite filter material and its preparation method are disclosed. The thermoplastic filter material with a diameter of 50-300 nanometers dispersed with nano-active particles is obtained by the method of melt blending and spinning. Polymer nanofibers improve the adsorption performance and filtration performance of the nanofiber itself, but it is difficult to effectively control the bulk density of the fiber during the formation of the nanofiber membrane. In the invention patent with the application number CN201510118169.1, an organic-inorganic composite nanofiber membrane filter material and its preparation method are disclosed. Organic nanofibers and inorganic micro-particles are fully mixed and dispersed in ethanol through an emulsifier to form a uniform The dispersion system ensures that the fibers and particles can be evenly distributed in the three-dimensional direction of the nanofiber membrane. The addition of micron particles is conducive to the adsorption of more particles, but the functionality of micron particles is limited. The invention patent with the application number CN201710331127.5 discloses a preparation method of a nanofiber porous membrane loaded with highly active nano-metal particles, which improves the antibacterial performance of the nanofiber porous membrane, but the operation method is complicated and the process is cumbersome.

Contents of the invention

In view of the above-mentioned deficiencies, the object of the present invention is to provide a nanofiber with a nano-protrusion structure on the surface and a preparation method thereof. Specifically, thermoplastic polymers and nanoparticles are melt-blended to prepare nanoparticle/thermoplastic polymer composites, and then the resulting composites are blended with cellulose acetate butyrate in proportion to melt spinning to obtain nanoparticles/thermoplastic polymers/CAB three cellulose acetate butyrate is removed by solvent extraction to prepare nanoparticle/thermoplastic polymer composite nanofibers, and then soaked in a specific solvent to obtain nanofibers with nano-protruding structures on the surface. The prepared surface contains nanofibers with nano-protrusion structure, the three-dimensional structure is stable, and the properties of adsorption, filtration, catalysis, and antibacterial are significantly improved.

In order to achieve the above object, the technical solution of the present invention is:

The first aspect of the present invention is a nanofiber with a nanoprotrusion structure on its surface. The nanofibers are composed of thermoplastic polymer nanofibers and nanoparticles protruding from their surfaces, and the components are in the following mass percentages: thermoplastic polymer: 60% to 99%, nanoparticles: 1% to 40%; The diameter of the nanoparticles is 1-50nm, and the diameter of the nanofibers is 50-350nm.

Preferably, the thermoplastic polymer is one or more of PVA-co-PE, PP, PA, PET, PBT, PTT, PMMA.

Preferably, the nanoparticles are a mixture of one or more of nano-oxide particles, nano-metal particles, and nano-polymer particles, and have a higher melting point than the thermoplastic polymer.

Preferably, the nanofibers have potential applications in fields such as filtration, adsorption, catalysis, and antibacterial.

A second aspect of the present invention is a method for preparing nanofibers whose surface contains nano-protrusion structures, specifically comprising the following steps:

S1, first melt blending thermoplastic polymers and nanoparticles to prepare nanoparticle/thermoplastic polymer composites;

S2. Blending, melting and spinning the compound obtained in step S1 and cellulose acetate butyrate (CAB) in a predetermined ratio to obtain nanoparticle/thermoplastic polymer/CAB ternary composite fiber;

S3. Reflowing the composite fiber obtained in step S2 to remove CAB to obtain nanoparticle/thermoplastic polymer composite nanofiber;

S4. Treating the nanoparticle/thermoplastic polymer composite nanofiber obtained in step S3 with a solvent to obtain a nanofiber material with a nano-protrusion structure on the surface.

Preferably, the blending and melting treatment described in step S2 specifically comprises extruding and granulating the compound through a twin-screw extruder at a temperature of 140-240° C. to obtain a nanoparticle/thermoplastic polymer/CAB ternary composite material.

Preferably, the mass percent of the nanoparticle/thermoplastic polymer composite described in step S1 is 1% to 40%: 60% to 99%; the mass percent of the nanoparticle/thermoplastic polymer composite and CAB described in step S2 5% to 40%: 60% to 95%.

Preferably, the reflux treatment described in step S3 is specifically reflux in acetone at 40-60° C. for 6-72 hours to extract and remove CAB.

Preferably, the solvent described in step S4 is water, acetone, isopropanol, tert-butanol, n-butanol, benzene, toluene, xylene, phenol, formic acid, acetic acid, sulfuric acid, methylene chloride, chloroform, dimethyl One or more of formamides.

Preferably, the solvent treatment described in step S4 is specifically soaking in a solvent at 30-100° C. for 10-120 min.

Technical idea of the present invention is in:

First, cellulose acetate butyrate is used as the sea phase, and the composite masterbatch of nanoparticles/thermoplastic polymer melt blending is used as the island phase. After melt blending, extrusion and drawing, cellulose acetate butyrate is uniformly dispersed in the nanoparticles /thermoplastic polymer composite, so that the nanoparticle/thermoplastic polymer composite is dispersed into a nanofibrous structure that cannot form a continuous phase, when acetone extraction removes cellulose acetate butyrate, the nanoparticle/thermoplastic polymer with a porous structure composite nanofibers.

Due to the removal of cellulose acetate butyrate by phase separation, the modified thermoplastic polymer nanofibers are obtained, and then soaked in a solvent to make a large number of nanoparticles form nano-protruding structures on the surface of the nanofibers. By controlling the soaking temperature and time , solvent type, etc., adjust the diameter of the nanofiber and the degree of the nano-protrusion, adjust the microstructure of the nanofiber, and then realize the regulation of the performance of the nanofiber. The obtained nanofibers have a nano-bulge structure, a stable three-dimensional structure, and nanoparticles with different properties can be firmly loaded on the thermoplastic nanofibers, which significantly increases the specific surface area of the nanofibers; It has small pore size and large porosity, and is loaded with nanoparticles with different properties, so that the nanofibers have excellent properties such as filtration, adsorption, catalysis, and antibacterial.

Beneficial effect

1. In the present invention, the nanoparticles and the thermoplastic polymer are uniformly mixed first, then granulated, drawn, and spun, and finally soaked in a specific solvent to obtain nanofibers with nano-protruding structures on the surface. This preparation method, nano The combination of particles and nanofibers is more stable and reliable, easier to post-processing and more stable in performance.

2. The present invention can regulate the microstructure of the nanofibers by controlling the soaking temperature, time, solvent type, etc., and then regulate the properties of the nanofibers.

3. The present invention removes cellulose acetate butyrate by phase separation to obtain thermoplastic polymer nanofibers, and then soaks them in a solvent to expose a large number of nanoparticles on the surface of the nanofibers to form a convex structure of nanoparticles, a three-dimensional structure It is stable and firmly loaded on thermoplastic nanofibers, which significantly increases the specific surface area of nanofibers; at the same time, because the diameter of the prepared nanofibers is 50-350nm, it has small pore size, large porosity, specific surface area, and active sites. The nanofiber has excellent properties such as filtration, adsorption, catalysis, antibacterial, etc., and overcomes the defects of the prior art.

4. The nano-protrusions on the surface of the nanofibers prepared by the present invention can be one or more kinds of nanoparticles, and the nanofibers with different properties can be prepared by controlling the morphology, size, content and type of the loaded nanoparticles; The diameter of the fiber is precisely controllable in the range of 50-350nm, and the prepared nanofiber has strong processability and stable structure.

5. The processes such as twin-screw extrusion granulation, melt spinning, and solvent immersion in the preparation method of the present invention are all physical processes, and the process is simple and easy to realize industrialization.

Description of drawings

Fig. 1 is an electron micrograph of a nanofiber with a nano-protrusion structure on the surface.

Detailed ways

The technical solutions of the various embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them; based on the embodiments of the present invention, All other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

The nano-titanium dioxide particles with an average particle size of 30nm and the PVA-co-PE masterbatch are mixed uniformly and dried at a mass ratio of 1:7 to prepare 3Kg of nano-titanium dioxide particles/PVA-co-PE composite materials; The composite material is uniformly mixed with 7Kg cellulose acetate butyrate (CAB), extruded and granulated in a twin-screw extruder with a processing temperature of 170°C, and 10Kg of nano-titanium dioxide particles/PVA-co-PE/ CAB composite material, and then the composite material is spun by a melt spinning machine to obtain a composite fiber; the composite fiber is refluxed in acetone at 58°C for 48 hours to extract cellulose acetate butyrate to obtain nano-titanium dioxide particles/PVA-co-PE The composite fibers were then soaked in 50°C isopropanol aqueous solution for 10 minutes, and dried at room temperature to prepare nano-titanium dioxide particles/PVA-co-PE composite nanofibers containing titanium dioxide nano-protruding structures, with an average diameter of 350 nm.

Example 2

Mix the nano-alumina particles with an average particle size of 30nm and the PP masterbatch at a mass ratio of 1:8 and dry to prepare 3Kg of nano-alumina particles/PP composite material; then mix 3Kg of the composite material with 8Kg butyl acetate Acid cellulose (CAB) was uniformly mixed, extruded and granulated in a twin-screw extruder at a temperature of 145°C to prepare a 11Kg nano-alumina/PP/CAB composite material, which was then processed by a melt spinning machine. The composite material was spun to obtain a composite fiber; the composite fiber was refluxed in acetone at 58°C for 50 hours to extract cellulose acetate butyrate to obtain a nano-alumina particle/PP composite fiber, and then soaked in xylene at 80°C for 40 minutes at room temperature. and dry under the hood to prepare nano-alumina particles/PP composite nanofibers containing alumina nano-protrusion structures, with an average diameter of 330 nm.

Example 3

Mix the nano-silica particles with an average particle size of 15nm and the PA masterbatch with a mass ratio of 2:9 and dry to prepare 1Kg of nano-silica particles/PA composite material; then mix 1Kg of the composite material with 4Kg Cellulose acetate butyrate (CAB) was uniformly mixed, extruded and granulated in a twin-screw extruder at a temperature of 210°C to prepare 5Kg of nano-silica particles/PA/CAB composite material, and then melted The spinning machine spins the composite material to obtain composite fibers; the composite fibers are refluxed in acetone at 58°C for 60 hours to extract cellulose acetate butyrate to obtain nano-silica particles/PA composite fibers, and then in 30°C formic acid aqueous solution Soak in medium for 10 minutes, dry at normal temperature, and prepare nano-silica particles/PA composite nanofibers containing silica nano-protrusion structure, with an average diameter of 320 nm.

Example 4

The nano zinc oxide particles with an average particle size of 20nm and the PET masterbatch are mixed uniformly and dried at a mass ratio of 1:10 to prepare 1Kg of nano zinc oxide particles/PET composite materials; then 1Kg of composite materials and 4Kg butyl acetate Acid cellulose (CAB) was uniformly mixed, extruded and granulated in a twin-screw extruder at a temperature of 240°C, and prepared to obtain 5Kg of nano-zinc oxide particles/PET/CAB composite material, and then passed through a melt spinning machine The composite material is spun to obtain a composite fiber; the composite fiber is refluxed in acetone at 58°C for 60 hours to extract cellulose acetate butyrate to obtain a nano-zinc oxide particle/PET composite fiber, and then mixed with xylene and n-butanol at 50°C Soak in the solution (V:V=7:3) for 30 minutes, and dry at room temperature to prepare nano-zinc oxide particles/PET composite nanofibers containing zinc oxide nano-protrusion structures, with an average diameter of 300 nm.

Example 5

The nano-copper particles with an average particle size of 20nm and the PBT master batch are mixed uniformly and dried at a mass ratio of 2:7 to prepare 1Kg of nano-copper particles/PBT composite material; (CAB) is uniformly mixed, extruded and granulated in a twin-screw extruder at a temperature of 190°C, and prepared to obtain 6Kg of nano-copper particles/PBT/CAB composite material, which is then compounded by a melt spinning machine The material is spun to obtain a composite fiber; the composite fiber is refluxed in acetone at 58°C for 62 hours to extract cellulose acetate butyrate to obtain a composite fiber of nano-copper particles/PBT composite material, and then soaked in phenol at 50°C for 20 minutes, and dried at room temperature , the nano-copper particle/PBT composite nanofiber containing the nano-copper particle convex structure was prepared, and the average diameter was 270nm.

Example 6

Mix nano-tungsten particles with an average particle size of 30nm and PTT masterbatch at a mass ratio of 1:6 and dry to prepare 1Kg of nano-tungsten particles/PTT composite material; then mix 1Kg of composite material with 6Kg of cellulose acetate butyrate (CAB) was uniformly mixed, extruded and granulated in a twin-screw extruder at a temperature of 220°C to prepare a 7Kg nano-tungsten particle/PTT/CAB composite material, which was then compounded by a melt spinning machine The material is spun to obtain a composite fiber; the composite fiber is refluxed in acetone at 58°C for 65 hours to extract cellulose acetate butyrate to obtain a nano-tungsten particle/PTT composite fiber, and then soaked in toluene at 80°C for 30 minutes, dried at room temperature, and prepared A nano-tungsten particle/PTT composite nanofiber with a raised structure containing nano-tungsten particles is obtained, with an average diameter of 250 nm.

Example 7

The nano-polystyrene particles with an average particle size of 20nm and the PVA-co-PE masterbatch are mixed uniformly and dried at a mass ratio of 1:10 to prepare a 1Kg nano-polystyrene particle/PVA-co-PE composite material; Then the composite material of 1Kg is uniformly mixed with 7Kg cellulose acetate butyrate (CAB), and extruded and granulated in a twin-screw extruder at a temperature of 170°C to prepare 8Kg of nano-polystyrene particles/PVA -co-PE/CAB composite material, and then the composite material is spun by a melt spinning machine to obtain a composite fiber; the composite fiber is refluxed in acetone at 58°C for 68 hours to extract cellulose acetate butyrate to obtain nano-polystyrene The particles/PVA-co-PE composite fibers were then soaked in 50°C isopropanol aqueous solution for 10 minutes, and dried at room temperature to prepare nano-polystyrene particles/PVA-co-PE composite nanostructures containing polystyrene nano-bulges. Fibers with an average diameter of 200 nm.

Example 8

Mix nano-titanium dioxide particles, nano-zinc oxide particles and PVA-co-PE masterbatch at a mass ratio of 1:1:10 and dry to prepare 3Kg of nano-titanium dioxide particles/nano-zinc oxide particles/PVA-co-PE composite Material; then the composite material of 3Kg is mixed evenly with 7Kg cellulose acetate butyrate (CAB), is extruded and granulated in a twin-screw extruder at a temperature of 170° C. to prepare 10 Kg of nano-titanium dioxide particles/nano Zinc oxide particles/PVA-co-PE/CAB composite material, and then the composite material is spun by a melt spinning machine to obtain a composite fiber; the composite fiber is refluxed in acetone at 58°C for 48 hours to extract cellulose acetate butyrate, Nano-titanium dioxide particles/nano-zinc oxide particles/PVA-co-PE composite nanofibers were obtained, then soaked in 50°C isopropanol aqueous solution for 10 minutes, and dried at room temperature to prepare nano-titanium dioxide particles/nano-zinc oxide containing nano-protruding structures Particle/PVA-co-PE composite nanofibers with an average diameter of 350nm.

Example 9

Mix nano-titanium dioxide particles, nano-zinc oxide particles, nano-silica particles and PVA-co-PE masterbatch at a mass ratio of 1:1:1:10 and dry to prepare 1Kg of nano-titanium dioxide particles/nano-zinc oxide Granules/nano silica particles/PVA-co-PE composite material; then 1Kg of composite material and 8Kg cellulose acetate butyrate (CAB) are uniformly mixed, and extruded in a twin-screw extruder at a temperature of 170°C out, granulated, and prepared 9Kg of nano-titanium dioxide particles/nanometer zinc oxide particles/nano-silicon dioxide particles/PVA-co-PE/CAB composite material, and then spun this composite material through a melt spinning machine to obtain composite fibers ; The composite fiber was refluxed in acetone at 58°C for 70 hours to extract cellulose acetate butyrate to obtain nano-titanium dioxide particles/nano-zinc oxide particles/nano-silicon dioxide particles/PVA-co-PE composite fibers, and then in 50°C isopropyl Soak in alcohol aqueous solution for 10min, dry at normal temperature, and prepare nano-titanium dioxide particles/nano-zinc oxide particles/nano-silicon dioxide particles/PVA-co- PE composite nanofibers with an average diameter of 150nm.

Example 10

Nano-titanium dioxide particles, nano-copper particles, nano-polystyrene particles and PVA-co-PE masterbatch are uniformly mixed and dried at a mass ratio of 1:1:1:10 to prepare 1Kg of nano-titanium dioxide particles/nano-copper particles/ Nano polystyrene particles/PVA-co-PE composite material; then 1Kg of composite material and 9Kg cellulose acetate butyrate (CAB) are uniformly mixed, and the temperature is extruded in a twin-screw extruder at 170°C. Granulating, preparing 10Kg of nano-titanium dioxide particles/nano-copper particles/nano-polystyrene particles/PVA-co-PE/CAB composite material, and then spinning this composite material through a melt spinning machine to obtain composite fibers; The fibers were refluxed in acetone at 58°C for 72 hours to extract cellulose acetate butyrate to obtain nano-titanium dioxide particles/nano-copper particles/nano-polystyrene particles/PVA-co-PE composite fibers, and then soaked in 50°C isopropanol aqueous solution 10min, dry at normal temperature, prepare the nano-titanium dioxide particle/nano-copper particle/nano-polystyrene particle/PVA-co-PE composite nanofiber containing nano-titanium dioxide particle, nano-copper particle, nano-polystyrene particle nano-bulge structure, The average diameter is 100 nm.

The nanofibers prepared in Examples 1-10 realize the loading of nanoparticles with different properties, and the surface presents a nano-shaped convex structure.

The present invention regulates the microstructure of the nanofiber by controlling the type of loaded nanoparticle, controlling the soaking temperature, time, solvent type, etc., and then regulates the performance of the nanofiber. The nanofibers with nano-protrusion structure on the surface prepared by the present invention are easy to process, and can control the shape and size of nano-protrusions, and can realize the loading of nanoparticles with different properties, and have potential in the fields of filtration, adsorption, catalysis, and antibacterial. application.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (10)

1. the nanofiber that nano projection structure is contained on a kind of surface, it is characterised in that: the nanofiber is by thermoplastic poly The nano particle composition of object nanofiber and its surface bulge is closed, and component presses following mass percent: thermoplastic polymer: 60%~99%, nano particle: 1%~40%；The nano-particle diameter be 1~50nm, the nanofiber it is straight Diameter is 50~350nm.

2. the nanofiber that nano projection structure is contained on surface according to claim 1, it is characterised in that: the thermoplastic Property polymer be one of PVA-co-PE, PP, PA, PET, PBT, PTT, PMMA or a variety of.

3. the nanofiber that nano projection structure is contained on surface according to claim 1, it is characterised in that: the nanometer Particle is one of nano-oxide particles, nano-metal particle, nanometer polymerization composition granule or a variety of mixing, and fusing point is higher than The thermoplastic polymer.

4. the nanofiber that nano projection structure is contained on surface according to claim 1, it is characterised in that: the nanometer Fiber can be applied to the fields such as filtering, absorption, catalysis, antibacterial.

5. the preparation method of the nanofiber of nano projection structure is contained on a kind of surface as described in claim 1, feature exists In: the following steps are included:

S1, thermoplastic polymer, nano particle melt blending be first prepared into nano particle/thermoplastic polymer composite；

S2, compound obtained by step S1 and acetylbutyrylcellulose (CAB) are handled by predetermined ratio blended melting and spinning, Obtain nano particle/thermoplastic polymer/CAB tri compound fiber；

S3, the composite fibre for obtaining step S2 carry out reflow treatment removal CAB, and it is multiple to obtain nano particle/thermoplastic polymer Close nanofiber；

S4, the nano particle/thermoplastic polymer composite nano fiber for obtaining step S3 are handled by solvent, are obtained surface and are contained There is the nano-fiber material of nano projection structure.

6. the preparation method of the nanofiber of nano projection structure, feature are contained in a kind of surface according to claim 5 Be: the processing of blended melting described in step S2 is to make compound by double screw extruder extrusion at 140~240 DEG C Grain, obtains nano particle/thermoplastic polymer/CAB trielement composite material.

7. the preparation method of the nanofiber of nano projection structure, feature are contained in a kind of surface according to claim 5 Be: nano particle/thermoplastic polymer composite mass percent described in step S1 be 1%~40%:60%~ 99%；The mass percent of nano particle/thermoplastic polymer composite and CAB described in step S2 are 5%~40%:60% ~95%.

8. the preparation method of the nanofiber of nano projection structure, feature are contained in a kind of surface according to claim 5 Be: reflow treatment described in step S3, the extraction in 6~72 hours that flows back specially in 40~60 DEG C of acetone remove CAB.

9. the preparation method of the nanofiber of nano projection structure, feature are contained in a kind of surface according to claim 5 Be: solvent described in step S4 be water, acetone, isopropanol, the tert-butyl alcohol, n-butanol, benzene,toluene,xylene, phenol, formic acid, One of acetic acid, sulfuric acid, methylene chloride, chloroform, dimethylformamide are a variety of.

10. the preparation method of the nanofiber of nano projection structure, feature are contained in a kind of surface according to claim 5 Be: the processing of solvent described in step S4 is specially to impregnate 10~120min in a solvent at 30~100 DEG C.