CN106243377B - A kind of porous silk fibrous material and preparation method thereof - Google Patents
A kind of porous silk fibrous material and preparation method thereof Download PDFInfo
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- CN106243377B CN106243377B CN201610690060.XA CN201610690060A CN106243377B CN 106243377 B CN106243377 B CN 106243377B CN 201610690060 A CN201610690060 A CN 201610690060A CN 106243377 B CN106243377 B CN 106243377B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0482—Elimination of a frozen liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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Abstract
The present invention relates to a kind of porous silk fiber and preparation method thereof, include the following steps: that (1) silk is placed in acid flux material and is sufficiently swollen；(2) the silk sample after being swollen is placed in swelling solvent carry out freezing processing below freezing；(3) freezing silk is placed in organic solvent or water and impregnates removal swelling solvent；(4) treated, and silk is freeze-dried to get porous silk fiber is arrived.Silk porous fibre is prepared by this method, equipment and technology is simple, operation influence factor is few, conducive to control, it is suitble to experimental study and mass production, and the porous silk fiber of preparation greatly improves the specific surface area of silk, porosity, reduces silk fibre densities, product can be used for the new technical fields such as organizational project, air filtration, medicament slow release.
Description
Technical field
The present invention relates to a kind of porous silk fibrous material and preparation method thereof, prepared material can be applied to regeneration doctor
The fields such as, air filtration, sewage treatment, drug loading.
Background technique
Silk (silk) is the secreted concretionary continuous fiber of silk liquid, also referred to as natural silk when matured silkworm cocoons, and is one
Kind natural fiber, earliest one of the animal origin of human use.According to archaeological discovery, China has utilized silk system about before 4700
Do silk thread, braided wires band and simple silk goods.Silkworm has silkworm, tussah, castor silkworm, cassava silkworm, willow silkworm and giant silkworm etc..By single
The strand that silk cocoon is pumped claims silk, and silk diameter is 5 ~ 20 μm.A piece silk borrows silk gum bonding to clad by two single fibers.
Every single fiber is made of more diameters in 0.01 ~ 0.4 μm of fibril.When filature, the silk of several silk cocoons is extracted out, it is viscous by means of silk gum
Synthetic threads are referred to as silk.The silk of silk gum is removed, nett silk is claimed.It is mulberry silk that dosage is maximum in silk, followed by tussah
Silk, other silks are because of the not formed resource of limited amount.Silk is light and elongated, and fabric sheen is good, comfortable and easy to wear, and feel is smooth rich
Full, moisture absorption is ventilative, referred to as fiber queen, is widely used in weaving various high-grade silks and satins and knitwear, and for industry, national defence
And medicine and other fields.China, Japan, India, the former Soviet Union and Korea are main Chan Si states, total output account for the 90% of world wide production with
On.
China is the major producing country of silk, and silk yield accounts for 70% of world wide production or more.Silk is derived from as one kind
The natural polymer biomaterial of nature has stable physico-chemical property, such as chemical stability and excellent mechanical property.Closely
Nian Lai, with going deep into silk structure and performance study, application is just prolonged from traditional field of textiles to high-technology field
It stretches, such as photoelectron and bio-medical material, has been achieved for impressive progress especially as bio-medical material.Silk is a kind of
Natural protein fibre, can be with natural degradation, and is mainly made of amino acid, wherein there is a large amount of polar amino acids, as glycine,
Tyrosine, asparatate, glutamic acid, threonine, serine etc..These polar amino acids are easier and heavy metal ion knot
It closes, therefore can be used for removal of heavy metal ions.Porous fibre because of large specific surface area, porosity is high, hole configurations is mutually communicated, molten
The advantages that matter diffusional resistance is small, be especially suitable for adsorbing and being separated by filtration material.However, silk is because of its stable materialization
Can, it there is no method that silk is modified at present or regenerate and be processed into porous fibre, which has limited silk fibers as filtering material
Using.Therefore, it finds a kind of simple and easy processing method and transform silk as fiber with porous structure to silk to more
The application and development in purposes field has great importance and development prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of simple, easy-operating porous silk fibrous material, and by this
The porous silk fibrous material of method preparation.
In order to achieve the above objectives, the present invention provides a kind of porous silk fibrous material preparation method, includes the following steps:
(1) Silk Soaking carries out swelling treatment in acid solution, obtains swelling silk；
(2) the swelling silk of step (1) is subjected to freezing processing, obtains frost silk；
(3) at a temperature of the freezing processing of step (2), by the frost silk of step (2) be placed in organic solvent or water into
Row immersion treatment, obtains Frozen Body；
(4) Frozen Body of step (3) is freeze-dried, obtains porous silk fibrous material.
In above-mentioned technical proposal, in step (1), silk can be mulberry silk, tussah silk, ricinus silk, wild silk yarn；Silk
Form can be silk, raw silk, twisted silk, woven fabric, knitted fabric.The present invention has pore-creating effect not only for single-silk,
For twisting thread, fabric etc. also can preferable pore-creating, obtain porous silk fibrous material.
In above-mentioned technical proposal, in step (1), acid is one of hydrochloric acid, formic acid, acetic acid, sulfuric acid, phosphoric acid, hydrofluoric acid
Or it is several；Acid concentration is 1~99 wt% in acid solution；The swelling treatment time is 1~10 minute.The present invention is using acid to silk
Swelling treatment is carried out without dissolving, so that adsorbing a large amount of solvent molecules inside silk and volume expansion occurring.
In above-mentioned technical proposal, in step (2), the temperature of freezing processing is the freezing temperature of step (1) acid solution；Swelling
Silk afterwards makes its internal solution freeze to form ice-nucleus and be filled in inside silk by freezing processing.
In above-mentioned technical proposal, in step (3), organic solvent is methanol, ethyl alcohol, isopropanol, chloroform, acetone, ether, ice
One of acetic acid, benzene, n-hexane, styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether, triethanolamine are several
Kind；The immersion treatment time is 6~28 hours.Organic solvent or water meeting when in frost silk merging organic solvent perhaps water
By the ice-nucleus displacement in Frozen Body, to form hole.
In the present invention, silk swelling treatment time in acid solution is 1~10 minute, is sufficiently swollen, silk adsorber acid is molten
Liquid saturation, quality no longer change, and it is uniform to facilitate the pore size distribution formed inside silk for sufficiently swelling, and avoids acid to silk
Energy slackens；The immersion treatment time is 6~28 hours, and abundant immersion treatment, organic solvent or water will freeze intracorporal ice-nucleus
(icing acid solution) is all replaced, and is on the one hand avoided acid residual from causing adverse effect, is on the other hand guaranteed good porosity；Again
Avoiding excessively impregnating causes silk performance to decline.Therefore the invention discloses the porous silk prepared according to above-mentioned preparation method fibres
Tie up material；The diameter of fiber is 1~100 μm in the porous silk fibrous material, and aperture is 10nm~10 μm；It can be applied to again
The fields such as raw medicine, air filtration, sewage treatment, drug loading.
Boiled silk is immersed in acid flux material by the present invention first, it may occur that is significantly swollen and is not dissolved, after swelling
The a large amount of acid solution of silk absorbed inside；In the carry out freezing processing below freezing of acid solution, promote the acid inside silk molten
Liquid freezes, and forms a large amount of ice-nucleus, obtains frost silk；It is maintained at after the freezing point of solvent, then frost Silk Soaking is had
Solvent or water replace the ice-nucleus inside silk to form hole；Freeze-drying process is carried out again, avoids hole dried
It collapses in journey, that is, forms silk porous fibre (referring to description of the invention attached drawing).Therefore, the invention discloses a kind of technique letters
Single, easy to operate preparation method realizes the porous structure preparation of silk fiber material for the first time, substantially increases the ratio of silk
Surface area has expanded the performance application of silk.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of porous silk fiber and natural silk made from embodiment one；
Fig. 2 is the scanning electron microscope (SEM) photograph of porous silk fiber made from embodiment two；
Fig. 3 is the scanning electron microscope (SEM) photograph of porous silk fiber made from embodiment three；
Fig. 4 is the X-ray diffraction spectrogram of porous silk fiber made from example IV；
Fig. 5 is the scanning electron microscope (SEM) photograph of porous silk fiber made from embodiment five；
Fig. 6 is the scanning electron microscope (SEM) photograph of porous silk fabric made from embodiment six；
Fig. 7 is the scanning electron microscope (SEM) photograph of porous silk fiber made from embodiment seven.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment one
(1) natural mulberry silk boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.5wt%, obtains after being repeated 3 times
Obtain degummed mulberry silk；
(2) boiled silk is soaked in 5 wt% hydrochloric acid and impregnates 30min, sufficiently swelling obtains swelling silk；
(3) swelling silk is placed in -20 DEG C of freezings, is subsequently placed in -20 DEG C of methanol and impregnates 24 hours, obtains Frozen Body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -20 DEG C.
Attached drawing 1 is the scanning electron microscope (SEM) photograph of above-mentioned porous silk fiber and untreated natural boiled silk fiber, and left figure is
Natural boiled silk fiber, right figure are above-mentioned porous silk fiber, and natural silk surface has no pore structure as seen from the figure, after processing
There are a large amount of micropores in silk surface.
Embodiment two
(1) natural mulberry silk boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.05wt%, obtains after being repeated 3 times
Obtain degummed mulberry silk；
(2) boiled silk is soaked in 10 wt% hydrochloric acid and impregnates 30min, obtain swelling silk；
(3) swelling silk is placed in -10 DEG C of freezings, is subsequently placed in -10 DEG C of 50wt% ethyl alcohol and impregnates 12 hours, obtains cold
Freeze body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -10 DEG C.
Attached drawing 2 is the scanning electron microscope (SEM) photograph of above-mentioned porous silk fiber, and silk table has a large amount of micropore knots after handling as seen from the figure
Structure generates.
Embodiment three
(1) natural mulberry silk boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.25wt%, obtains after being repeated 3 times
Obtain degummed mulberry silk；
(2) boiled silk is soaked in 30 wt% hydrofluoric acid and impregnates 30min, obtain swelling silk；
(3) swelling silk is placed in -80 DEG C of freezings, is subsequently placed in -80 DEG C of chloroforms and impregnates 24 hours, obtains Frozen Body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -80 DEG C.
Attached drawing 3 is the scanning electron microscope (SEM) photograph of above-mentioned porous silk fiber, and silk table has a large amount of micropore knots after handling as seen from the figure
Structure generates.
Example IV
(1) natural mulberry silk boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.05wt%, obtains after being repeated 3 times
Obtain degummed mulberry silk.
(2) boiled silk is soaked in 30 wt% formic acid and impregnates 30min, obtain swelling silk；
(3) swelling silk is placed in -10 DEG C of freezings, is subsequently placed in -10 DEG C of water and impregnates 48 hours, obtains Frozen Body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -10 DEG C.
Attached drawing 4 is the x-ray diffraction pattern of above-mentioned porous silk fiber, and the structure of porous silk fiber is main as seen from the figure
For II crystalline texture of Silk.
Embodiment five
(1) natural mulberry silk boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.25wt%, obtains after being repeated 3 times
Obtain degummed mulberry silk.
(2) boiled silk is soaked in 50wt% formic acid and impregnates 30min, obtain swelling silk；
(3) swelling silk is placed in -60 DEG C of freezings, is subsequently placed in -60 DEG C of isopropanols and impregnates 48 hours, is freezed
Body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -60 DEG C.
Attached drawing 5 is the scanning electron microscope (SEM) photograph of above-mentioned porous silk fiber, and silk table has a large amount of micropore knots after handling as seen from the figure
Structure generates.
Embodiment six
(1) natural real silk fabric boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.05wt%, after being repeated 3 times
Obtain degummed mulberry silk.
(2) degumming real silk fabric is soaked in 98wt% formic acid and impregnates 30min, obtain swelling silk；
(3) swelling silk fabric is placed in -40 DEG C of freezings, is subsequently placed in -40 DEG C of 10wt% acetic acid and impregnates 24 hours, obtains
To Frozen Body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -40 DEG C.
Attached drawing 6 is the scanning electron microscope (SEM) photograph of above-mentioned porous silk fabric, there is greatly silk fibroin dimension table after handling as seen from the figure
Microcellular structure is measured to generate.
Embodiment seven
(1) natural tussah silk boils 30min degumming with the sodium bicarbonate solution of mass fraction 0.5wt%, obtains after being repeated 3 times
Obtain degummed mulberry silk.
(2) boiled silk is soaked in 88 wt% formic acid and impregnates 30min, obtain swelling silk；
(3) swelling silk is placed in -20 DEG C of freezings, is subsequently placed in -20 DEG C of ethyl alcohol and impregnates 12 hours, obtains Frozen Body；
(4) Frozen Body that step (3) obtain is placed in freeze dryer and is freeze-dried into porous silk fiber for -20 DEG C.
Attached drawing 7 is the scanning electron microscope (SEM) photograph of above-mentioned porous silk fiber, and silk table has a large amount of micropore knots after handling as seen from the figure
Structure generates.
Claims (9)
1. a kind of preparation method of porous silk fibrous material, which comprises the steps of:
(1) Silk Soaking carries out swelling treatment in acid solution, obtains swelling silk；
(2) the swelling silk of step (1) is subjected to freezing processing, obtains frost silk；Freezing processing temperature is that step (1) acid is molten
The freezing temperature of liquid；
(3) at a temperature of the freezing processing of step (2), the frost silk of step (2) is placed in organic solvent or water and is soaked
Bubble processing, obtains Frozen Body；
(4) Frozen Body of step (3) is freeze-dried, obtains porous silk fibrous material.
2. the preparation method of porous silk fibrous material according to claim 1, it is characterised in that: in step (1), the silkworm
Silk is mulberry silk, tussah silk, ricinus silk or wild silk yarn；The silk is silk, raw silk, twisted silk, woven fabric or needle
Fabric.
3. the preparation method of porous silk fibrous material according to claim 1, it is characterised in that: in step (1), the acid
For one of hydrochloric acid, formic acid, acetic acid, sulfuric acid, phosphoric acid, hydrofluoric acid or several；In the acid solution acid concentration be 1~
99wt%。
4. the preparation method of porous silk fibrous material according to claim 1, it is characterised in that: described molten in step (1)
The swollen processing time is 1~10 minute.
5. the preparation method of porous silk fibrous material according to claim 1, it is characterised in that: described to have in step (3)
Solvent is methanol, ethyl alcohol, isopropanol, chloroform, acetone, ether, glacial acetic acid, benzene, n-hexane, styrene, perchloroethylene, trichlorine
One of ethylene, ethylene glycol ether, triethanolamine are several.
6. the preparation method of porous silk fibrous material according to claim 1, it is characterised in that: in step (3), the leaching
The bubble processing time is 6~28 hours.
7. the preparation method of porous silk fibrous material according to claim 1, it is characterised in that: cold in the step (4)
Freezing drying temperature is -80~10 DEG C.
8. porous silk prepared by the preparation method of any one porous silk fibrous material according to claims 1 to 7 is fine
Tie up material.
9. porous silk fibrous material according to claim 8, it is characterised in that: silkworm in the porous silk fibrous material
The diameter of silk fiber is 1~100 μm, and aperture is 10nm~10 μm.
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Families Citing this family (5)
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| CN106917266B (en) * | 2017-03-23 | 2019-12-17 | 宁波芸生纺织品科技有限公司 | antibacterial natural silk fiber product and preparation method thereof |
| CN106835688B (en) * | 2017-03-23 | 2019-12-17 | 宁波芸生纺织品科技有限公司 | Antibacterial silk fibroin fiber and preparation method thereof |
| CN109440202B (en) * | 2018-10-18 | 2023-09-08 | 青岛即发集团股份有限公司 | Wet spinning vacuum freeze-drying method and drying equipment |
| CN110485154B (en) * | 2019-08-28 | 2022-03-29 | 安徽迪惠新材料科技有限公司 | Preparation method of silk fabric with excellent antibacterial property |
| CN113736134B (en) * | 2021-11-08 | 2022-02-22 | 国家电投集团氢能科技发展有限公司 | Modified expanded polytetrafluoroethylene, preparation method thereof, composite ion exchange membrane and application thereof |
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| JP2000045173A (en) * | 1998-05-22 | 2000-02-15 | Tamaki:Kk | Fiber having porous structure or hydrophilicity, or modification of fabric comprising the same fiber |
| CN102397592A (en) * | 2010-09-17 | 2012-04-04 | 卢爱军 | Dipping technology of protein strings |
| CN102008756A (en) * | 2010-12-10 | 2011-04-13 | 苏州大学 | Preparation method of nano-fibrous silk fibroin-based porous scaffold |
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