CN113058445B - Preparation method of bamboo charcoal fiber/silk fibroin-based fiber composite membrane - Google Patents
Preparation method of bamboo charcoal fiber/silk fibroin-based fiber composite membrane Download PDFInfo
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- CN113058445B CN113058445B CN202110249594.XA CN202110249594A CN113058445B CN 113058445 B CN113058445 B CN 113058445B CN 202110249594 A CN202110249594 A CN 202110249594A CN 113058445 B CN113058445 B CN 113058445B
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- silk fibroin
- bamboo charcoal
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- membrane
- based fiber
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- 239000000835 fiber Substances 0.000 title claims abstract description 133
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 98
- 239000012528 membrane Substances 0.000 title claims abstract description 80
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 58
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 58
- 241001330002 Bambuseae Species 0.000 title claims abstract description 58
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 58
- 239000011425 bamboo Substances 0.000 title claims abstract description 58
- 239000003610 charcoal Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 26
- 239000004626 polylactic acid Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- MBDICAOEPMIKPN-UHFFFAOYSA-L calcium ethanol dichloride hydrate Chemical group O.C(C)O.[Cl-].[Ca+2].[Cl-] MBDICAOEPMIKPN-UHFFFAOYSA-L 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- JYISHPYSHUCRGU-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;urea Chemical compound NC(N)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O JYISHPYSHUCRGU-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000004378 air conditioning Methods 0.000 abstract description 2
- 239000002562 thickening agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000009987 spinning Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000007630 basic procedure Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000520 microinjection Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method of a bamboo charcoal fiber/silk fibroin-based fiber composite membrane, which comprises the following steps: (1) Preparing a silk fibroin-based fiber membrane, and slightly dissolving the silk fibroin-based fiber membrane; (2) Preparing bamboo charcoal fiber dispersion, dipping the slightly-dissolved silk fibroin-based fiber membrane into the bamboo charcoal fiber dispersion, taking out and drying to obtain the bamboo charcoal fiber/silk fibroin-based fiber composite membrane. The invention utilizes a micro-dissolving method to dissolve the silk fibroin to form a natural thickener, so that the bamboo charcoal fiber is easy to be adsorbed on the surface of the composite membrane, thereby endowing the silk fibroin composite membrane with antibacterial property and simultaneously ensuring that the bamboo charcoal fiber and the silk fibroin substrate have better adhesion fastness; the method is environment-friendly and high in economic benefit, and the prepared membrane has good antibacterial performance and is expected to be applied to the fields of masks, air-conditioning filtration and the like.
Description
Technical Field
The invention relates to a preparation method of a biomass composite antibacterial filtering membrane, in particular to a preparation method of a bamboo charcoal fiber/silk fibroin-based fiber composite membrane.
Background
The silk fibroin is a natural polymer material, is easy to obtain, economical, environment-friendly and degradable. The production process of the polylactic acid is pollution-free and biodegradable, realizes the circulation in nature, and is an ideal green high polymer material. At present, silk fibroin/polylactic acid composite materials are concerned by more and more researchers, and due to the combination of the two materials, the respective advantages can be exerted, and the respective disadvantages can be overcome. However, the composite material of the two has no antibacterial property, which limits further application thereof.
The bamboo charcoal fiber has unique cellular micropore structure and excellent moisture permeability and air permeability which are not possessed by other fibers, can absorb moisture in a short time and maintain the dryness of the bamboo charcoal fiber, so that microorganisms are not easy to grow, namely the bamboo charcoal fiber has good inhibition effect on bacteria. In addition, the bamboo charcoal fiber can absorb, decompose peculiar smell and deodorize dust and harmful substances such as lampblack smell, formaldehyde, benzene, toluene, ammonia and the like, and has super strong adsorption and deodorization functions.
Researchers often adsorb the antibacterial substance on the surface of the material by a common impregnation method, and the antibacterial substance on the material obtained by the method is easy to fall off from the surface of the material due to weak bonding force with a base material.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a bamboo charcoal fiber/silk fibroin-based fiber composite membrane with strong binding force.
The technical scheme is as follows: the preparation method of the bamboo charcoal fiber/silk fibroin-based fiber composite membrane comprises the following steps:
(1) Preparing a silk fibroin-based fiber membrane, and slightly dissolving the silk fibroin-based fiber membrane;
(2) Preparing bamboo charcoal fiber dispersion, dipping the slightly-dissolved silk fibroin-based fiber membrane into the bamboo charcoal fiber dispersion, taking out and drying to obtain the bamboo charcoal fiber/silk fibroin-based fiber composite membrane.
Preferably, in the step (1), the porosity change rate of the surface of the slightly-dissolved silk fibroin-based fiber membrane is less than or equal to 1%; when the content is more than 1%, the slightly-soluble fiber is too strong to cause too much damage to the fiber structure, and only the porosity change rate is in the range, so that on one hand, the appearance of the fiber is not greatly influenced, and on the other hand, the bamboo charcoal fiber is more favorably adhered to the silk fibroin-based fiber membrane; the time for slightly dissolving is 1-10 min; when the size is more than 10mim, the shape damage of the fiber is large, and when the size is less than 1min, the slightly dissolving effect is small; the temperature of the micro-dissolution is 25-40 ℃, and the micro-dissolution can be promoted in the temperature range.
Preferably, a dissolving agent is dripped on the surface of the silk fibroin-based fiber membrane for slightly dissolving, wherein the dissolving agent is a calcium chloride-ethanol-water system, an ethylene diamine tetraacetic acid-urea system or a lithium bromide water solution system. On one hand, the dissolving agent can only dissolve silk fibroin without influencing another component in the silk fibroin-based fiber membrane and destroying the mechanical structure of the component, and on the other hand, the dissolving degree of the dissolving agent in the process of dissolving the silk fibroin is controllable, and the dissolving agent is neither too violent nor too slow.
Preferably, in the step (1), a dissolving agent is dripped on the surface of the silk fibroin-based fiber membrane for slightly dissolving, and the dripping amount of the dissolving agent is only required to be sufficient for infiltrating the surface of the silk fibroin-based fiber membrane, preferably the whole surface; the dissolving agent is a calcium chloride-ethanol-water system, and the molar ratio of the calcium chloride to the ethanol to the water is 0.1-1.
Preferably, when the dissolving agent is an ethylene diamine tetraacetic acid-urea system, the slightly dissolving time is 0-20min; wherein, the proportion of the urea in the ethylene diamine tetraacetic acid-urea system is 10wt%, and the preferable slightly-dissolving time is 40 ℃; when the dissolving agent is a lithium bromide aqueous solution system, the slightly-dissolving time is 0-20min, wherein the concentration of the lithium bromide aqueous solution is 9.3mol/L, and the slightly-dissolving time is preferably 40 ℃.
Preferably, in the step (2), the slightly-dissolved silk fibroin-based fiber membrane is immersed in the bamboo charcoal fiber dispersion liquid for 10-60 min; when the dipping time is less than 10min, the load amount of the bamboo charcoal fiber is too small, and when the dipping time is more than 60min, the influence of continuously increasing the dipping time on the adsorption of the bamboo charcoal fiber is small.
Preferably, in the step (2), the bamboo charcoal fiber is ground and then dispersed in water to form a bamboo charcoal fiber dispersion liquid, the concentration of the bamboo charcoal fiber dispersion liquid is 50-500 mg/L, and within the concentration range, the bamboo charcoal fiber can be well dispersed.
Preferably, in step (1), the silk fibroin-based fiber membrane is a silk fibroin/polylactic acid fiber membrane, a silk fibroin/polycaprolactone fiber membrane, or a silk fibroin/polyglycolic acid fiber membrane.
Preferably, in the step (1), the silk fibroin-based fiber membrane is a silk fibroin/polylactic acid fiber membrane, the mass ratio of the silk fibroin to the polylactic acid is 0.5-5, when the mass ratio is greater than 5, the mechanical property of the material is reduced, and when the mass ratio is less than 0.5, the slightly-dissolving effect is poor.
Preferably, in the step (1), the specific method for preparing the silk fibroin-based fiber membrane comprises the following steps:
(1.1) dissolving the degummed silk in a lithium bromide aqueous solution, centrifuging, filtering and dialyzing to obtain a silk fibroin aqueous solution, and freeze-drying to obtain silk fibroin;
(1.2) dissolving silk fibroin and polyester polymer to form mixed spinning solution, and then preparing a silk fibroin-based fiber membrane by using an electrostatic spinning method; the concentration of the mixed spinning solution is 4-30 wt%; the conditions of the electrostatic spinning method are as follows: the spinning voltage is 14-20 kV, the receiving distance from the needle to the receiver is 10-15 cm, the extrusion speed of the micro-injection pump is 0.6-1.2 mL/h, the ambient temperature is 15-30 ℃, and the humidity is 40-60 RH%.
Preferably, the silk fibroin-based fiber membrane is treated by using an ethanol aqueous solution before the micro-dissolution of the silk fibroin-based fiber membrane, wherein the volume fraction of the ethanol aqueous solution is 70-90%, and the treatment time is 30-40 min.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: 1. a micro-dissolving method is utilized to dissolve a small amount of silk fibroin to form a natural thickener, so that the bamboo charcoal fiber is easy to adsorb on the surface of the composite membrane, and the bamboo charcoal fiber and the silk fibroin substrate have good adhesion fastness while the antibacterial property of the silk fibroin composite membrane is endowed. 2. The method is environment-friendly and high in economic benefit, and the prepared membrane has good antibacterial performance and is expected to be applied to the fields of masks, air-conditioning filtration and the like.
Detailed Description
The present invention is described in further detail below.
Example 1
(1) Dissolving degummed silk in a lithium bromide aqueous solution, centrifuging, filtering, dialyzing to obtain a silk fibroin aqueous solution, and freeze-drying at-50 ℃ for 2 days to obtain silk fibroin;
(2) Respectively dissolving silk fibroin and polylactic acid in hexafluoroisopropanol solvent to prepare mixed spinning solution; the mass ratio of the silk fibroin to the polylactic acid is 0.5, and the concentration of the spinning solution is 20wt%; preparing a silk fibroin/polylactic acid composite fiber membrane by adopting an electrostatic spinning method;
wherein, the conditions of the electrostatic spinning method are as follows: the spinning voltage is 20kV, the receiving distance from the needle to the receiver is 10cm, the extrusion speed of the micro-injection pump is 1.0mL/h, the ambient temperature is 30 ℃, and the humidity is 45RH%;
(3) Carrying out aftertreatment on the fibroin/polylactic acid composite fiber membrane for 30min at 37 ℃ by adopting ethanol with the volume fraction of 80%;
(4) Dropwise adding a calcium chloride-ethanol-water solution on the surface of the treated silk fibroin/polylactic acid fiber membrane, wherein the molar ratio of calcium chloride-ethanol-water is 0.1; grinding the bamboo charcoal fiber by a homogenizer, and uniformly dispersing the bamboo charcoal fiber in water by ultrasonic, wherein the concentration of the bamboo charcoal fiber in water is 50mg/L;
(5) Soaking the silk fibroin/polylactic acid fiber membrane after standing in the bamboo charcoal fiber aqueous solution for 10min; taking out, washing with deionized water, and air drying to obtain bamboo charcoal fiber/silk fibroin/polylactic acid fiber composite membrane.
Example 2
The basic procedure is the same as in example 1, except that: the mass ratio of the silk fibroin to the polylactic acid is 1, and the concentration of the spinning solution is 15wt%; performing aftertreatment on the fibroin/polylactic acid composite fiber membrane for 10min at 37 ℃ by adopting ethanol with the volume fraction of 90%; dropwise adding calcium chloride-ethanol-water solution on the surface of the silk fibroin/polylactic acid fiber membrane, and standing for 10min at 25 ℃; the molar ratio of calcium chloride to ethanol to water is 1.
Example 3
The basic procedure is the same as in example 1, except that: the mass ratio of the silk fibroin to the polylactic acid is 2, and the concentration of the spinning solution is 30wt%; carrying out aftertreatment on the fibroin/polylactic acid composite fiber membrane for 40min at 37 ℃ by adopting ethanol with the volume fraction of 70%; dropwise adding calcium chloride-ethanol-water solution on the surface of the silk fibroin/polylactic acid fiber membrane, and standing for 1min at 40 ℃; the molar ratio of calcium chloride to ethanol to water is 0.5.
Example 4
The basic procedure is the same as in example 1, except that: the mass ratio of the silk fibroin to the polylactic acid is 5, and the concentration of the spinning solution is 4wt%; the concentration of the bamboo charcoal fiber in water is 500mg/L, and the silk fibroin/polylactic acid fiber membrane after standing is soaked in the bamboo charcoal fiber dispersion liquid for 30min.
Example 5
The basic procedure is the same as in example 1, except that: and respectively dissolving silk fibroin and polycaprolactone in a hexafluoroisopropanol solvent to prepare a mixed spinning solution.
Example 6
The basic procedure is the same as in example 1, except that: respectively dissolving silk fibroin and polyglycolic acid in hexafluoroisopropanol solvent to prepare mixed spinning solution.
Comparative example 1
The basic procedure is the same as in example 1, except that: soaking the silk fibroin/polylactic acid fiber membrane treated by ethanol in the water solution of bamboo charcoal fiber.
Comparative example 2
The basic procedure is the same as in example 1, except that: dropwise adding calcium chloride-ethanol-water solution, and standing for 20min.
Comparative example 3
The basic procedure is the same as in example 1, except that: and dripping ethylene diamine tetraacetic acid-urea solution on the surface of the silk fibroin/polylactic acid fiber membrane.
The porosity of the surfaces of the silk fibroin/polylactic acid fiber membranes before and after the slightly dissolution in the above examples 1 to 6 and comparative examples 2 and 3 was measured, and the results are shown in tables 1 and 2.
The porosity and mass loss of the bamboo charcoal fiber/silk fibroin-based fiber composite membrane samples prepared in the above examples 1 to 6 and comparative examples 1 to 3 were measured, and the results are shown in tables 3 and 4.
TABLE 1 porosity data of silk fibroin-based fiber membrane surface before and after micro-dissolution for each example
Table 2 porosity data of silk fibroin-based fiber membrane surface before and after comparative examples 2 and 3 slightly dissolving
TABLE 3 porosity and loss of bamboo carbon fiber quality data for each example sample
TABLE 4 porosity and loss of bamboo carbon fiber in each comparative sample
As can be seen from tables 1 and 2, when the method of the present invention is used to perform micro-dissolution on the silk fibroin-based fiber membrane, a small amount of silk fibroin can be dissolved under appropriate conditions, and the change of the porosity of the silk fibroin-based fiber membrane before and after micro-dissolution is small, which indicates that the micro-dissolution has no great influence on the morphology of the fiber.
As can be seen from tables 3 and 4, the porosity of the bamboo charcoal fiber/silk fibroin-based fiber composite membrane prepared by the method of the present invention is still in a relatively suitable range, which indicates that the bamboo charcoal fiber/silk fibroin-based fiber composite membrane still has a suitable microporous structure, thereby facilitating the moisture permeability and air permeability of the composite membrane. Meanwhile, the mass loss rate of the bamboo charcoal fiber can be known, and the slightly dissolving can promote the adhesion of the bamboo charcoal fiber on the silk fibroin-based composite membrane under the proper slightly dissolving condition, so that the bamboo charcoal fiber and the silk fibroin substrate have better adhesion fastness, and the antibacterial property of the bamboo charcoal fiber is fully exerted.
Claims (6)
1. A preparation method of a bamboo charcoal fiber/silk fibroin-based fiber composite membrane is characterized by comprising the following steps:
(1) Preparing a silk fibroin-based fiber membrane, and slightly dissolving the silk fibroin-based fiber membrane; in the step (1), the temperature of the slightly dissolving is 25-40 ℃; the time for slightly dissolving is 1-10 min; dripping a dissolving agent on the surface of the silk fibroin-based fiber membrane for slightly dissolving, wherein the dissolving agent is a calcium chloride-ethanol-water system, an ethylene diamine tetraacetic acid-urea system or a lithium bromide water solution system; the silk fibroin-based fiber membrane is a silk fibroin/polylactic acid fiber membrane, a silk fibroin/polycaprolactone fiber membrane or a silk fibroin/polyglycolic acid fiber membrane;
(2) Preparing bamboo charcoal fiber dispersion liquid, dipping the silk fibroin-based fiber membrane after slight dissolution in the bamboo charcoal fiber dispersion liquid, taking out and drying to obtain the bamboo charcoal fiber/silk fibroin-based fiber composite membrane.
2. The method for preparing bamboo charcoal fiber/silk fibroin-based fiber composite membrane according to claim 1, wherein in step (1), the porosity change rate of the surface of the slightly-solubilized silk fibroin-based fiber membrane is less than or equal to 1%.
3. The method for preparing the bamboo charcoal fiber/silk fibroin-based fiber composite membrane according to claim 1, wherein in the step (1), a dissolving agent is dropwise added to the surface of the silk fibroin-based fiber membrane for slightly dissolving, wherein the dissolving agent is a calcium chloride-ethanol-water system, and the molar ratio of the calcium chloride to the ethanol to the water is 0.1-1.
4. The method for preparing the bamboo charcoal fiber/silk fibroin-based fiber composite membrane according to claim 1, wherein in the step (2), the slightly-dissolved silk fibroin-based fiber membrane is immersed in the bamboo charcoal fiber dispersion liquid for 10-60 min.
5. The method for preparing the bamboo charcoal fiber/silk fibroin-based fiber composite membrane according to claim 1, wherein in the step (2), the bamboo charcoal fiber is ground and then dispersed in water to form a bamboo charcoal fiber dispersion liquid, and the concentration of the bamboo charcoal fiber dispersion liquid is 50-500 mg/L.
6. The preparation method of the bamboo charcoal fiber/silk fibroin-based fiber composite membrane according to claim 1, wherein in the step (1), the silk fibroin-based fiber membrane is a silk fibroin/polylactic acid fiber membrane, and the mass ratio of the silk fibroin to the polylactic acid is 0.5-5.
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JP2003253557A (en) * | 2002-03-01 | 2003-09-10 | Akebono Toba | Fiber material having excellent deodorization and absorption of far infrared ray and organic chlorine compound, its fiber product and method for producing the same |
CN105686159A (en) * | 2016-03-14 | 2016-06-22 | 浙江大学 | Method for preparing novel mask chip by utilizing fibroin plate cocoons |
CN107574494A (en) * | 2017-08-31 | 2018-01-12 | 常州欧康铭化工有限公司 | A kind of preparation method of antibacterial air-filtering fiber |
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