CN107083674B - A kind of preparation method of silk nanofiber dispersion liquid - Google Patents
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Abstract
The invention discloses a kind of preparation method of silk nanofiber dispersion liquid, silk fiber is pre-processed through formic acid first, then carries out oxidation processes, is obtained finally by decentralized processing with the silk nanofiber dispersion liquid for stablizing nanofibrous structures.Carboxylic group with electronegativity is introduced natural silk fiber by oxidation processes by the present invention, and the mode for being aided with mild mechanical dispersion realizes the efficient preparation for retaining the single-silk nanofiber dispersion liquid of preferable prototype structure.Silk nanofiber prepared by the present invention has pH responsiveness simultaneously, and the precipitation and separation and redisperse of silk nanofiber can be realized by the regulation to pH value, convenient for storage and transport, and has very big potential utility value in correlation function material building field.
Description
Technical field
The invention belongs to nano-cellulose technical fields, are related to the preparation method of silk nanofiber and its dispersion liquid preparation
Technical field, and in particular to aoxidize silk fiber using a kind of oxidation system, and prepare silk nanofiber in conjunction with mechanical treatment
The method of dispersion liquid.
Background technique
In nature, animal silk is aroused widespread concern and interest with its excellent comprehensive mechanical property.So
And can not show a candle to the true mechanical property of fibroin itself from silk mechanical property obtained in silk cocoon, this is because curley waste
The process and the subsequent process to silk fiber of silk have seriously affected each level structure of silk fiber.Therefore, people are always
The imitated research of silk is dedicated to, wherein obtaining structure and the more complete silk egg of performance reservation from natural silk fiber
White material is always the key points and difficulties of the area research.It is worth noting that, fibroin is with spontaneous in silk fiber
A kind of natural hierarchical structure that nanofiber assembles, although the silk fiber (such as mulberry silk and tussah silk) of separate sources exists
Different from amino acid sequence, however its hierarchical structure is essentially identical.Therefore artificial material is being constructed using fibroin
When, researchers' expectation retains these natural formations and character to greatest extent, in order to construct the silk of excellent in mechanical performance
Nanofiber functional material.
Animal creates the unique close, labyrinth of silk-fibroin in evolution in 1 years, from natural silk fiber
Stripping nano structure is faced with many difficulties, therefore is rarely reported.Although by spin processes prepared by the silk protein solution after regeneration
Have much at the method for fibre structure, but on the silk fiber performance that obtains of this kind of mode and pattern and in natural silk fiber
Fine structure has very big difference, not discusses herein.For current research, though by removing or being partly dissolved natural silk
The Structure of Silk of nano-scale can be so obtained, but because of the limitation of preparation method, the silk nanofiber of acquisition exists
Structural instability, size distributing inhomogeneity and the defects such as yield is low.The 90th phase of document Appl. Phys. Lett. in 2007 is reported
Road " Ultrasonic technique for extracting nanofibers from nature materials ", is adopted
Nanofibers can be removed from natural silk with the mode being ultrasonically treated by force, however the nanofiber separated is wrapped around one another
It is not easy to the building of material；The 2nd phase of document J. Mater. Chem. B in 2014 reports " Silk dissolution
And regeneration at the nanofibril scale " is partly dissolved natural silkworm by formic acid/calcium chloride system
Silk fiber, acquisition nanofibrous structures are unstable in a solvent and can not operate in water phase；China Patent Publication No.
CN104532365 A, publication date is on April 22nd, 2015, entitled " a kind of preparation method of silk nanofiber "
The silk aggregation with nanotopography can be obtained in such a way that infiltration is aided with long-time mechanical treatment, but this mode
The silk fiber of acquisition is wrapped around one another closely gluey for class water-setting, does not have single pattern and surface electronegativity, in addition by from
The heart can settle；The 28th phase of Adv. Mater. in 2016 reports entitled " Liquid Exfoliated Natural Silk
Nanofi brils:Applications in Optical and Electrical Devices " passes through simply engaging portion
Divide the method for dissolution and ultrasonic disperse, obtained silk nanofiber yield is lower.Therefore develop a kind of efficiently prepare with steady
It is very necessary for determining the method for the silk nanofiber of nanofibrous structures.
Summary of the invention
Goal of the invention: for the low disadvantage of the existing structural instability of fibroin nanofiber preparation and yield, this hair
It is bright that the preparation method of a kind of silk nanofiber and its dispersion liquid is provided, with the means modified silk fiber of oxidation, and it is aided with light
The efficient preparation with the single-silk nanofiber for stablizing nanofibrous structures is realized in micromechanics processing.
Technical solution: to realize the above goal of the invention, The technical solution adopted by the invention is as follows:
A kind of preparation method of silk nanofiber dispersion liquid, silk fiber are pre-processed through formic acid first, then carry out oxygen
Change processing, obtains finally by decentralized processing with the silk nanofiber dispersion liquid for stablizing nanofibrous structures.
The formic acid pretreatment, the concentration of formic acid are greater than 30%wt, processing 0.5 ~ 72.
The oxidation processes chemical oxidizing agent or (and) biological enzyme oxidant.
The chemical oxidizing agent is any one of hypohalogenous acids, hypohalite, hydrogen peroxide, ozone, peracid；Described
Biological enzyme agent is any one of hydrogen peroxide and oxidation enzymatic mixture, laccase, peroxidase, and oxidant is preferably secondary
Sodium chlorate.
The decentralized processing is mechanical dispersion processing.
The silk includes mulberry silk, tussah silk, spider silk and other silks.
The preparation method silk nanofiber dispersion liquid obtained of the silk nanofiber dispersion liquid.
The silk nanofiber dispersion liquid has pH responsiveness, can realize silk nanometer by the adjusting of pH value
Fiber precipitation and separation, and redisperse becomes the stable silk nanofiber dispersion liquid of performance.
A kind of silk nanofiber obtained from the silk nanofiber dispersion liquid, carboxyl-content is relative to institute
State 0.3 mmol/g or more of the weight of silk nanofiber.
The silk nanofiber, which is characterized in that the diameter of the silk nanofiber is 50-500 nm, length
It is 10 μm of 50 nm-.
The utility model has the advantages that compared with prior art, the present invention is introduced the carboxylic group with electronegativity by oxidation processes
Natural silk fiber, the mode for being aided with mild mechanical dispersion realize the silk nanofiber dispersion liquid for retaining preferable prototype structure
Efficient preparation.Silk nanofiber prepared by the present invention has pH responsiveness simultaneously, can be realized by the regulation to pH value
The precipitation and separation and redisperse of silk nanofiber convenient for storage and transport, and have pole in correlation function material building field
Big potential utility value.
Detailed description of the invention
Fig. 1 is silk nanofiber transmission electron microscope picture；Wherein, left figure is silkworm nanofiber, and right figure is tussah Nanowire
Dimension；
Fig. 2 is mulberry silk nanofiber oxidation front and back titration curve figure；Left figure is original mulberry silk fiber titration curve, right
Figure is mulberry silk fiber titration curve after oxidation；
Fig. 3 is that silk nanofiber precipitates redisperse phenomenon at different pH；Left figure is mulberry silk nanofiber, and right figure is
Tussah silk nanofiber.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further elaborated.Embodiment is sent out for illustrative and not limiting
It is bright.For any those of ordinary skill in this field it will be appreciated that these embodiments are not limit the invention in any way, it is appropriate to do
Modification and without prejudice to essence of the invention and deviate the scope of the present invention.
In following embodiment, used measuring method is as follows: oxidation silk fiber carboxyl-content measurement: by 0.1 g oxygen
Silk fiber after change is added in 60 mL distilled water, and stirring 30 min by magnetic rotor makes suspension be uniformly dispersed；With 0.1
The pH of mixed system is adjusted to 3 and stablizes 5min by M HCl；0.05M NaOH is then added dropwise to mixing with the speed of 0.1mL/min
The pH of system is 11.The electric conductivity value variation and consumed NaOH dosage for recording mixed system in the above process, pass through titration
Curve calculates carboxyl-content.
Embodiment 1: the formic acid processing of boiled silk fiber
Take silk fiber after 10g degumming, be added with the solid-to-liquid ratio of 1:20 in the formic acid solution of 30 wt%, impregnate after 48 h from
The heart separates silk fiber and formic acid solution.By silk fiber wash with distilled water to neutral in case using；It is molten that centrifugation obtains formic acid
Liquid may be reused.
Embodiment 2: the formic acid processing of boiled silk fiber
Take silk fiber after 10 g degummings, be added with the solid-to-liquid ratio of 1:20 in the formic acid solution of 80 wt%, impregnate after 2 h from
The heart separates silk fiber and formic acid solution.By silk fiber wash with distilled water to neutral in case using；It is molten that centrifugation obtains formic acid
Liquid may be reused.
Embodiment 3: hypochlorite oxidation prepares silk nanofiber
It weighs 1 g formic acid treated that silk fiber is scattered in 100 mL distilled water, 0.1 mM NaClO is added, with
The stirring of 200 r/min speed, maintaining pH is 10 1 h of lower room temperature reaction.Use 0.5 mol/L HCl by system pH after reaction
It is adjusted to neutrality, is centrifuged 10 min with 10000 r/min, sediment fraction is centrifuged repeatedly cleaning 5 times.Water-insoluble fraction quality at this time
The rate of recovery is 95.9%.Water-insoluble fraction is placed in 100 mL deionized waters the ultrasound 2 under 19.5 kHz, 300 W power
Min is repeated 5 times；It is silk nanofiber dispersion liquid that centrifugation, which obtains supernatant fraction,.
Embodiment 4: hypochlorous acid oxidization prepares silk nanofiber
It weighs 1 g formic acid treated that silk fiber is scattered in 100 mL distilled water, 15 mM HClO are added, with 200
The stirring of r/min speed, maintaining pH is 10 1 h of lower room temperature reaction.System pH is adjusted using 0.5 mol/L HCl after reaction
To neutrality, 10 min are centrifuged with 10000 r/min, sediment fraction is centrifuged repeatedly cleaning 5 times.Water-insoluble fraction mass recovery at this time
Rate is 58.6%.Water-insoluble fraction is placed in 100 mL deionized waters 2 min of ultrasound under 19.5 kHz, 300 W power, weight
It is 5 times multiple；It is silk nanofiber dispersion liquid that centrifugation, which obtains supernatant fraction,.
Embodiment 5: hypochlorite oxidation prepares silk nanofiber
1 g formic acid is weighed treated silk fiber, is added in 100 mL distilled water and is sufficiently stirred, keep silk fiber abundant
Dispersion.15 mM NaClO are added to be aoxidized at room temperature, with the stirring of 200 r/min speed, maintaining pH is 10 2 h of lower reaction.
System pH is adjusted to neutrality using 0.5 mol/L HCl after reaction, is centrifuged 10 min, precipitation section with 10000 r/min
Divide and is centrifuged repeatedly cleaning 5 times；Water-insoluble fraction mass recovery is 73.3% at this time.By water-insoluble fraction be placed in 100 mL go from
In sub- water under 19.5 kHz, 300 W power 2 min of ultrasound, be repeated 5 times；It is silk nanometer that centrifugation, which obtains supernatant fraction,
Fiber dispersion.
Embodiment 6: hypochlorite oxidation prepares silk nanofiber
1 g formic acid is weighed treated silk fiber, is added in 100 mL distilled water and is sufficiently stirred, keep silk fiber abundant
Dispersion.30 mM NaClO are added to be aoxidized at room temperature, with the stirring of 200 r/min speed, maintaining pH is 10 2 h of lower reaction.
System pH is adjusted to neutrality using 0.5 mol/L HCl after reaction, is centrifuged 10 min, precipitation section with 10000 r/min
Divide and is centrifuged repeatedly cleaning 5 times；Water-insoluble fraction mass recovery is 50.2% at this time.By water-insoluble fraction be placed in 100 mL go from
In sub- water under 19.5 kHz, 300 W power 2 min of ultrasound, be repeated 5 times；It is silk nanometer that centrifugation, which obtains supernatant fraction,
Fiber dispersion.
Embodiment 7: silk nanofiber dispersion liquid precipitate redisperse
50 mL silkworm nanofiber dispersion liquid are taken, dispersion liquid pH is adjusted to 5, must be sunk with 5000 r/min centrifuging and takings
Shallow lake part, being calculated separately by constant weight method and obtaining the moisture of precipitating is 20.6%, and solid recovery rate is 80.1% at this time.
By the silk nanofiber mixed system pH precipitated under acid condition by 0.05 M NaOH be adjusted to pH 7 with
On；Or after being centrifugated aqueous precipitate, 10 min of magnetic agitation in distilled water, can make the silk nanometer of precipitating again
Fiber re-forms the dispersion liquid of stable uniform.
Embodiment 8: silk nanofiber dispersion liquid precipitate redisperse
50 mL silkworm nanofiber dispersion liquid are taken, dispersion liquid pH is adjusted to 3, must be sunk with 5000 r/min centrifuging and takings
Shallow lake part, being calculated separately by constant weight method and obtaining the moisture of precipitating is 21.2%, and solid recovery rate is 93.6% at this time.
By the silk nanofiber mixed system pH precipitated under acid condition by 0.05 M NaOH be adjusted to pH 7 with
On；Or after being centrifugated aqueous precipitate, 10 min of magnetic agitation in distilled water, can make the silk nanometer of precipitating again
Fiber re-forms the dispersion liquid of stable uniform.
Embodiment 9: silk nanofiber performance measurement
Silk nanofiber prepared by above-described embodiment 4 is selected to carry out performance measurement, as a result as follows:
1) silk nanofiber transmission electron microscope picture as shown in Figure 1, left figure is mulberry silk nanofiber, receive for tussah silk by right figure
Rice fiber.As shown in Figure 1, the nanofiber dispersion of this oxidation system preparation is uniform, and the diameter of silk nanofiber is in 100 nm
Left and right and length can achieve several microns.
2) mulberry silk titration curve variation in oxidation front and back is as shown in Fig. 2, left figure is original mulberry silk fiber titration curve, the right side
Figure is mulberry silk fiber titration curve after oxidation.It can be seen that oxidation process obviously increases carboxyl-content generation in silk fiber.
3) silk nanofiber precipitate redisperse phenomenon at different pH as shown in figure 3, left figure be mulberry silk nanofiber,
Right figure is tussah silk nanofiber.From figure can no matter mulberry silk or tussah silk nanofiber, have at acidic bright
Aobvious deposited phenomenon, and as pH replys neutrality, it can be separated into the nanofiber dispersion liquid of stable homogeneous again.
Claims (7)
1. a kind of preparation method of silk nanofiber dispersion liquid, which is characterized in that silk fiber is pre-processed through formic acid first, so
After carry out oxidation processes, obtain finally by decentralized processing with stablizing the silk nanofiber dispersion liquid of nanofibrous structures；
The oxidation processes chemical oxidizing agent or/and biological enzyme oxidant；The decentralized processing is mechanical dispersion processing；It is described
Chemical oxidizing agent be any one of hypohalogenous acids, hypohalite, hydrogen peroxide, ozone, peracid；The biological enzyme agent
For any one of hydrogen peroxide and oxidation enzymatic mixture, laccase, peroxidase.
2. the preparation method of silk nanofiber dispersion liquid according to claim 1, which is characterized in that the formic acid is located in advance
The concentration of reason, formic acid is greater than 30%wt, handles 0.5~72h.
3. the preparation method of silk nanofiber dispersion liquid according to claim 1, which is characterized in that the silk packet
Include mulberry silk, tussah silk.
4. the preparation method of silk nanofiber dispersion liquid according to claim 1 is obtained to have the single silkworm of electronegativity
Silk nanofiber dispersion liquid.
5. silk nanofiber dispersion liquid according to claim 4, which is characterized in that the silk nanofiber dispersion
Liquid has pH responsiveness, silk nanofiber precipitation and separation can be realized by the adjusting of pH value, and redisperse becomes performance
Stable silk nanofiber dispersion liquid.
6. a kind of silk nanofiber obtained from silk nanofiber dispersion liquid as claimed in claim 4, which is characterized in that
The carboxyl-content of the silk nanofiber is the 0.3mmol/g or more of the weight relative to the silk nanofiber.
7. silk nanofiber according to claim 6, which is characterized in that the diameter of the single-silk nanofiber is
50-500nm, length are 50nm-10 μm.
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| CN109957848A (en) * | 2019-02-28 | 2019-07-02 | 常州市协旺纺织品有限公司 | A kind of preparation method of modification regeneration fibroin fiber |
| CN112442190B (en) * | 2019-08-29 | 2022-04-01 | 武汉大学 | Preparation method of silk nano material |
| CN113818238B (en) * | 2021-08-24 | 2022-07-12 | 南京林业大学 | Preparation method and application of functional fibroin nanofiber, dispersion liquid and composite material |
| CN114703651A (en) * | 2022-03-14 | 2022-07-05 | 安徽农业大学 | Method for extracting silk micro/nano fibers through oxidation modification and application of silk micro/nano fibers |
| CN115354408A (en) * | 2022-08-17 | 2022-11-18 | 西南大学 | Preparation method, product and application of nano tussah silk fiber |
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| CN103013137B (en) * | 2011-09-20 | 2016-06-08 | 于仁毅 | The preparation of albumen silkworm silk and the application in cosmetics |
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| Original Silk Pre-oxidationg Treatment of Carbon Fiber from Coal Tar Pitch;xuefei zhao et al;《Advanced Materials Research》;20140716;194-198页 * |
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