CN107556761A - A kind of graphene/silk/salix monogolica nano composite material and preparation method thereof - Google Patents
A kind of graphene/silk/salix monogolica nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene/silk/salix monogolica nano composite material and preparation method thereof, step is as follows：Salix monogolica is removed the peel, crushed, is sieved, is dried, is cooled down, purify after obtain salix cellulose；Salix cellulose is modified using sodium metaperiodate；Silk/salix monogolica magnetic porous composite material is obtained using liquid nitrogen, freeze-drying process；Final impregnating reuses reducing agent reduction and finally gives graphene/silk/salix monogolica nano composite material in graphene oxide solution.The method comprises the steps of firstly, preparing the three-dimensional porous composite of magnetic silk/salix monogolica, and then using three-dimensional porous composite as base material, graphene is carried out into effective self assembly, finally gives graphene/silk/salix monogolica nano composite material.The composite possesses many advantages, such as green, good mechanical property, institutional framework are regular, porosity is high, repeatable utilization, there is important application value in fields such as sewage disposal, photoelectric devices.
Description
Technical field
The present invention relates to a kind of graphene/silk/salix monogolica nano composite material, belongs to field of nanocomposite materials.
Background technology
Silk is described as fiber queen, and its is soft, abundant, smooth, plentiful, possesses gloss soft as pearl,
Weaving, apparel industry are widely used.Silk is made up of silk gum and fibroin, and wherein silk gum is located at the outer layer of silk, content
Between 20%-30%, fibroin is located at the internal layer of silk, and content is between 70%-80%.Fibroin positioned at silk internal layer is one
Kind natural macromolecular material, by serine（serine）, glycine（Glycine）, alanine（alanine）Deng 18 kinds of amino
Acid composition, molecular weight is about 2300kDa, is made up of heavy chain, light chain and P25, and wherein the molecular weight of heavy chain H chains is 350kDa, gently
Chain L chain molecular weights are 26kDa, and P25 molecular weight is 30kDa, and the ratio of three is 6:6:1.Fibroin share 11 noncrystalline domains and
12 crystal regions, by disulfide bond between heavy chain H chains and light chain L chains, form H-L complexs.
The crystal habit of fibroin is broadly divided into two kinds of the type of fibroin I and II type of fibroin.The type of fibroin I is a kind of knot of meta-stable
Structure, conformation are crank shape or zigzag, are a kind of intermediatenesses between alpha-helix and beta sheet, and structure cell belongs to orthorhombic
System.Handled through damp and hot, sour, polar solvent etc., the type of fibroin I is easy to change to the type of fibroin II.The type of fibroin II is antiparallel β-folding
Stack structure, belong to orthorhombic system, peptide chain arranged regular, hydrogen bond and intermolecular gravitation make adjacent chain is intersegmental to be tightly combined, tension
It is strong to stretch ability, and is insoluble in water, it is strong to the resistance of acid, alkali, salt, enzyme and heat.In addition, recent years are found that one kind is new again
Fibroin crystal habit, i.e. the type of fibroin III, its crystal structure is similar with polyglycine II, belongs to hexagonal crystal system.
Silk obtained regenerated silk fibroin after degumming, dissolving, purification have nontoxic, non-stimulated, biological degradability,
Biocompatibility, good engineering properties, are easily processed into various forms, as silk protein films, gel, fiber, three-dimensional rack,
Sponge etc., it is a kind of important natural function material, available for fields such as biology, medical science, photoelectric materials, is carried as medicament slow release
Body, tissue engineering bracket, operation suture thread, artificial skin, artificial tendon, cell culture vector, wound dressing, electrically conducting transparent are thin
Film, sorbing material etc.（Silk, 2017,03:6-12；Biomedical engineering magazine, 2015,06:1364-1368；Sericulture section
Learn, 2016,02:341-345）.
For a long time, cellulose is always weaving, the key industry raw material of papermaking, with its recyclability, biodegradable
Property and cost advantage are increasingly subject to the attention of people, in medicine control, release tech, immobilization technology, biology sensor, membrane material
Material, performance chemicalses and additive etc. show good development prospect.Reduction and oil, natural gas due to arable land etc.
The increasingly depleted of fossil resource, the yield of synthetic fibers will be restricted more and more.And a kind of green of cellulose conduct,
Environmentally friendly, reproducible resource, obtain a unprecedented opportunity to develop.
Salix monogolica is the desert plant that a kind of only a few can be grown in salt-soda soil.Its sprout is yellow, in leaf is linear or line
Shape lanceolar, branch, which is grown thickly, is not afraid of husky pressure, and well developed root system, rudiment power is strong, is desert-control tree, be mainly distributed on the Inner Mongol,
The ground such as Hebei, Shanxi, Shaanxi, Gansu, Qinghai, Sichuan.Salix monogolica is one of the first choice of " three Norths shelter-forest ", is not only acted as windproof solid
Effect that is husky, conserving water and soil, improving the ecosystem, maintaining ecological balance etc. that also there is unique function.
Salix monogolica in addition to small part is used for pulping and paper-making, fiberboard and composite plate, burn or lose as yule logs by the overwhelming majority
Abandon, cause the huge wasting of resources.The main chemical compositions of salix monogolica mainly have cellulose, hemicellulose, lignin and ash content, fine
The content of element is tieed up in more than 60-70%, is natural reproducible biomass resource, rationally will produce huge warp using salix monogolica resource
Benefit of helping and ecological benefits.At present, most research all concentrates on the cellulose how extracted in salix monogolica.Beijing Forestry University
Department of chemistry engineering Jiang builds new et al. the influence that have studied steam blasting pretreatment to salix monogolica composition and fibre structure performance（Modernization
Work, 2008,28 (2)）.Agricultural University of the Inner Mongol's material science and School of Art and Design Zhang Bin et al. are using salix cellulose as original
Material, have studied the technique that supercritical ultrasonics technology prepares microfibril（Paper and papermaking, 2014,33 (3)）.Agricultural University of the Inner Mongol's material science
With refined et al. main chemical compositions cellulose, the hemicelluloses that salix monogolica material has been isolated using chemical reagent of School of Art and Design Li Ya
Element（Agricultural University of the Inner Mongol's journal, 2014,35 (1)）.Industry light industry textile industry institute of Qiqihar University is permitted phoenix et al. and utilizes peroxidating
Hydrogen method separates salix monogolica and the cellulose in caragana microphylla mixed material（Chemistry of forest product and industry, 2006,26 (2)）.Zhengzhou University's chemical industry
Salix cellulose is extracted with energy institute Huang star et al. use acid catalysis Ethanol Method（Jiangsu's agriculture science, 2014,42 (3)）.
And the document that salix monogolica based nano composite material is prepared using the salix cellulose of extraction as raw material is less.Such as the Inner Mongol
Agriculture university Li Ya is refined to report salix cellulose/composite titania material（Li Ya is refined, and salix celluloses/titanium dioxide is multiple
The preparation of condensation material and performance study [D] Agricultural University of the Inner Mongol, 2015）.Chinese patent CN201410701957.9 is disclosed
A kind of salix monogolica regenerated celulose fibre, Chinese patent CN201410544845.7 disclose a kind of nanometer silver antimicrobial salix monogolica again
Raw cellulose fibre, Chinese patent CN201410544055.9 disclose a kind of feature salix monogolica regenerated celulose fibre and its system
Preparation Method, Chinese patent CN201410544166.X disclose a kind of graphene blending salix monogolica regenerated celulose fibre and its preparation
Method.
2004, Univ Manchester UK physicist An Deliehaimu and Constantine's Nuo Woxiao loves, utilize
The method for tearing adhesive tape, successfully isolates the graphene of individual layer atomic arrangement from graphite, therefore two people also obtain 2010
The Nobel Prize in physics in year（Science,2004,306( 5696):666-669）.Graphene is by carbon atom with sp2Hydridization rail
Road forms hexangle type honeycomb lattice, and its construction unit is carbon hexatomic ring, and it is a kind of two-dimentional material of only single layer of carbon atom thickness
Material.Graphene is the basic system unit for forming carbon-based material.It can be wrapped to form zero dimension Fullerenes, be rolled into one-dimensional
Carbon nanotube, layer upon layer is into three-dimensional graphite.From graphene find that day, graphene just into
For the focus and focus of research, in ultracapacitor, transparency electrode, desalinization, light emitting diode, sensor, hydrogen storage, the sun
The fields such as energy battery, catalyst carrier, composite, biologic bracket material, bio-imaging, drug delivery, weaving, printing and dyeing have extensively
General application（Novel charcoal material, 2014,05:329-356, Chinese invention patent 201410565512.2）.
Graphene composite material is research direction important in graphene application field（Chemical Engineer, 2015,01:34-
38+46）.Existing graphene composite material is by graphene oxide and another material mostly（Inorganic material, polymeric material
Material etc.）Uniformly it is mixed in solvent, finished product is then obtained by the methods of spin processes, vacuum filtration, spin coating.But due to graphene
The problem of certain be present in the π-π stackings effect easily aggregation of itself, its dispersiveness in a solvent（Chemical progress, 2016,05:
647-656）, the preparation of follow-up composite and the final performance of product can be influenceed.
The content of the invention
In view of the above problems, the present invention provides a kind of graphene/silk/salix monogolica nano composite material and preparation method thereof.
The technical scheme is that：
（1）Salix monogolica is removed the peel, crushed, crosses 50-100 mesh sieves, 80-100 DEG C of drying, cooling obtains salix wood powder, then by salix monogolica
Wood powder is added in autoclave, adds absolute ethyl alcohol-acetic acid mixture, bath raio 1:10, wherein the acetic acid addition is
3-5%wt, after being heated to 100-160 DEG C, 1-5h is stirred, is cooled down, filtering, is washed 2-5 times with absolute ethyl alcohol, then use deionized water
Rinse well repeatedly, drying obtains salix cellulose.（2）Salix cellulose in step 1 is scattered in deionized water, bathed
Than 1:50,1-20g/L sodium metaperiodate is then added, lucifuge reacts 30-60min at 50-80 DEG C, repeatedly clear with deionized water
Wash, centrifuge, drying obtains sodium metaperiodate and is modified salix cellulose.（3）Silk-fibroin is dissolved in deionized water, is configured to 1g/L-
The 100g/L aqueous solution, the 1g/L-100g/L trivalent iron salt aqueous solution is slowly dropped into silk-fibroin under conditions of 50-80 DEG C
In the aqueous solution, stir, wherein the mass ratio of the silk-fibroin and trivalent iron salt is 1:1-10:1, with 30 drops/min speed
The calcium chloride solution that concentration is 1-5wt% is added dropwise, regulation pH value to 10-12, after 60 DEG C are at the uniform velocity stirred 1h, is slowly added to walk
Sodium metaperiodate in rapid two is modified salix cellulose, after ultrasonic mixing is uniform, pours into mould, is put into 1min in liquid nitrogen, takes out
After be placed in pre-freeze 6h in -20 DEG C of refrigerators, freeze 6h in -80 DEG C of Thermo ultra low temperature freezers, be then placed in 48h in freeze dryer and obtain
To magnetic porous composite material.（4）Configuration concentration 0.1-100g/L graphene oxide water solution, ultrasonic 1h, by step 3
Magnetic porous composite material be immersed in 10-120min in graphene oxide solution, bath raio 1:50, it is anti-with ethanol and deionized water
After multiple cleaning, vacuum drying.（5）After the dipping of repeat step four-drying course 1-10 times, it is placed in reductant solution and is gone back
Original, is cleaned repeatedly with ethanol and deionized water, and graphene/silk/salix monogolica nano composite material is obtained after vacuum drying.
Preferably, the silk-fibroin is that silk is made after degumming, dissolving, dialysis, purification；
Preferably, the trivalent iron salt is the one or more in iron chloride, ferric sulfate, ferric nitrate；
Preferably, the mass ratio of the calcium chloride and silk-fibroin is 1:10-1:50.
Preferably, the mass ratio of the modified salix cellulose and silk-fibroin is 1:10-10:1.
Preferably, the reducing agent is that hydrazine hydrate, sodium borohydride, sodium citrate, vitamin C, hydroiodic acid, tea are more
One or more in phenol.
Compared with prior art, the advantage of the invention is that：
（1）Cellulose fibre is extracted using salix monogolica, raw material is sufficient, cheap, improves the utilization rate of salix monogolica resource, solves
Salix monogolica in addition to small part is used for pulping and paper-making, fiberboard and composite plate, burn or abandon as yule logs, causes by the overwhelming majority
The problem of huge wasting of resources, certain economic benefit and ecological benefits will be produced.（2）Sodium metaperiodate is modified to a certain extent
The crystal region of salix cellulose is destroyed, cellulose macromolecule produced expanded, swelling, weakened in salix cellulose macromolecular
Portion's structure lateral connection, strand orientation are destroyed, and crystallinity declines, so as to be advantageous to be grafted on salix cellulose macromolecular chain
Silk-fibroin functional group, be advantageous to composite porous formation and the infiltration of nano particle.（3）Be modified salix cellulose and
Silk-fibroin is carrier, generates nano ferriferrous oxide granule, and obtain porosity after crosslinking, liquid nitrogen, freeze-drying process
Extremely abundant three-dimensional porous silk-salix monogolica composite, final load graphene, ensure that graphene in silk-salix monogolica base
The Stability Analysis of Structures and mechanical strength of dispersing uniformity and graphene/silk/salix monogolica nano composite material in body.（4）Graphene/
Silk/salix monogolica nano composite material has certain magnetic, it is possible to achieve effective to recycle.
Embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1：
（1）Salix monogolica is removed the peel, crushed, crosses 50 mesh sieves, 80 DEG C of drying, cooling obtains salix wood powder, then adds salix wood powder
Into autoclave, absolute ethyl alcohol-acetic acid mixture, bath raio 1 are added:10, wherein acetic acid addition is 3%wt, is heated to
After 100 DEG C, 1h is stirred, is cooled down, filtering, is washed 2 times with absolute ethyl alcohol, then is rinsed well repeatedly with deionized water, drying obtains
Salix cellulose.（2）Salix cellulose in step 1 is scattered in deionized water, bath raio 1:50, then add 10g/L's
Sodium metaperiodate, lucifuge reacts 30min at 50 DEG C, is cleaned repeatedly with deionized water, centrifuges, and drying obtains sodium metaperiodate and is modified sand
Willow cellulose.（3）Silk-fibroin is dissolved in deionized water, is configured to the 20g/L aqueous solution, by 10g/L's under conditions of 50 DEG C
Ferric chloride in aqueous solution is slowly dropped into silk protein aqueous solution, is stirred, wherein the mass ratio of the silk-fibroin and iron chloride
For 1:1, calcium chloride solution of the concentration as 1wt% is added dropwise using 30 drops/min speed, the mass ratio of calcium chloride and silk-fibroin is
1:10, after regulation pH value at the uniform velocity stirs 1h to 10,60 DEG C, the sodium metaperiodate being slowly added in step 2 is modified salix cellulose,
The mass ratio of wherein modified salix cellulose and silk-fibroin is 1:1, after ultrasonic mixing is uniform, pour into mould, be put into liquid nitrogen
1min, pre-freeze 6h in -20 DEG C of refrigerators is placed in after taking-up, 6h is freezed in -80 DEG C of Thermo ultra low temperature freezers, be then placed in lyophilized
48h obtains magnetic porous composite material in machine.（4）Configuration concentration 1g/L graphene oxide water solution, ultrasonic 1h, by step 3
In magnetic porous composite material be immersed in 10min in graphene oxide solution, bath raio 1:50, with ethanol and deionized water repeatedly
After cleaning, vacuum drying, 90 DEG C of reductase 12 h in hydrazine hydrate solution are placed in, are cleaned repeatedly with ethanol and deionized water, be dried in vacuo
After obtain graphene/silk/salix monogolica nano composite material.
Embodiment 2：
（1）Salix monogolica is removed the peel, crushed, crosses 80 mesh sieves, 90 DEG C of drying, cooling obtains salix wood powder, then adds salix wood powder
Into autoclave, absolute ethyl alcohol-acetic acid mixture, bath raio 1 are added:10, wherein acetic acid addition is 4%wt, solid-to-liquid ratio
1:10, after being heated to 120 DEG C, 2h is stirred, is cooled down, filtering, is washed 3 times with absolute ethyl alcohol, then is rinsed repeatedly with deionized water dry
Only, drying obtains salix cellulose.（2）Salix cellulose in step 1 is scattered in deionized water, bath raio 1:50, then
15g/L sodium metaperiodate is added, lucifuge reacts 45min at 65 DEG C, is cleaned repeatedly with deionized water, centrifuges, and drying obtains height
Sodium iodate is modified salix cellulose.（3）Silk-fibroin is dissolved in deionized water, is configured to the 30g/L aqueous solution, 60 DEG C of condition
It is lower that 40g/L ferric sulfate aqueous solution is slowly dropped into silk protein aqueous solution, stir, wherein the silk-fibroin and sulphur
The mass ratio of sour iron is 1:1, calcium chloride solution of the concentration as 2wt%, calcium chloride and silk egg are added dropwise using 30 drops/min speed
White mass ratio is 1:20, after regulation pH value at the uniform velocity stirs 1h to 11,60 DEG C, the sodium metaperiodate being slowly added in step 2 is modified
Salix cellulose, wherein the mass ratio of modified salix cellulose and silk-fibroin is 1:2, after ultrasonic mixing is uniform, pour into mould,
1min in liquid nitrogen is put into, pre-freeze 6h in -20 DEG C of refrigerators is placed in after taking-up, freezes 6h in -80 DEG C of Thermo ultra low temperature freezers, then
It is put into 48h in freeze dryer and obtains magnetic porous composite material.（4）Configuration concentration 5g/L graphene oxide water solution, ultrasound
1h, the magnetic porous composite material in step 3 is immersed in 30min in graphene oxide solution, bath raio 1:50, with ethanol and
After deionized water is cleaned repeatedly, vacuum drying；（5）After dipping-drying course 2 times of repeat step four, it is placed in sodium citrate
90 DEG C of reduction 12h, are cleaned, the nano combined material of graphene/silk/salix monogolica are obtained after vacuum drying repeatedly with ethanol and deionized water
Material.
Embodiment 3：
（1）Salix monogolica is removed the peel, crushed, crosses 100 mesh sieves, 100 DEG C of drying, cooling obtains salix wood powder, then adds salix wood powder
It is added in autoclave, adds absolute ethyl alcohol-acetic acid mixture, bath raio 1:10, wherein acetic acid addition is 5%wt, solid-liquid
Than 1:20, after being heated to 160 DEG C, 5h is stirred, is cooled down, filtering, is washed 5 times with absolute ethyl alcohol, then rinsed repeatedly with deionized water
Totally, drying obtains salix cellulose.（2）Salix cellulose in step 1 is scattered in deionized water, bath raio 1:50, with
20g/L sodium metaperiodate is added afterwards, and lucifuge reacts 60min at 80 DEG C, is cleaned repeatedly with deionized water, centrifuges, and drying obtains
Sodium metaperiodate is modified salix cellulose.（3）Silk-fibroin is dissolved in deionized water, is configured to the 100g/L aqueous solution, 80 DEG C
Under the conditions of 100g/L iron nitrate aqueous solution is slowly dropped into silk protein aqueous solution, stir, wherein the silk-fibroin
Mass ratio with ferric nitrate is 1:1, calcium chloride solution of the concentration as 5wt% is added dropwise using 30 drops/min speed, calcium chloride with
The mass ratio of silk-fibroin is 1:50, after regulation pH value at the uniform velocity stirs 1h to 12,60 DEG C, the sodium metaperiodate that is slowly added in step 2
The mass ratio of modified salix cellulose, modified salix cellulose and silk-fibroin is 2:1, after ultrasonic mixing is uniform, pour into mould,
1min in liquid nitrogen is put into, pre-freeze 6h in -20 DEG C of refrigerators is placed in after taking-up, freezes 6h in -80 DEG C of Thermo ultra low temperature freezers, then
It is put into 48h in freeze dryer and obtains magnetic porous composite material.（4）Configuration concentration 80g/L graphene oxide water solution, ultrasound
1h, the magnetic porous composite material in step 3 is immersed in 60min in graphene oxide solution, bath raio 1:50, with ethanol and
After deionized water is cleaned repeatedly, vacuum drying；（5）After dipping-drying course 5 times of repeat step four, it is placed in sodium borohydride
60 DEG C of reduction 5h, are cleaned, the nano combined material of graphene/silk/salix monogolica are obtained after vacuum drying repeatedly with ethanol and deionized water
Material.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.Here all embodiments can not be exhaustive.It is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is amplified out still in protection scope of the present invention.
Claims (7)
- A kind of 1. preparation method of graphene/silk/salix monogolica nano composite material, it is characterised in that：Step 1：Salix monogolica is removed the peel, crushed, crosses 50-100 mesh sieves, 80-100 DEG C of drying, cooling obtains salix wood powder, then will Salix wood powder is added in autoclave, adds absolute ethyl alcohol-acetic acid mixture, bath raio 1:10, wherein the acetic acid adds Measure as 3-5%wt, after being heated to 100-160 DEG C, stir 1-5h, cool down, filtering, washed 2-5 times with absolute ethyl alcohol, then spend from Sub- water is rinsed well repeatedly, and drying obtains salix cellulose；Step 2：Salix cellulose in step 1 is scattered in deionized water, bath raio 1:50, then add 1-20g/L's Sodium metaperiodate, lucifuge reacts 30-60min at 50-80 DEG C, is cleaned repeatedly with deionized water, centrifuges, and drying obtains sodium metaperiodate Modified salix cellulose；Step 3：Silk-fibroin is dissolved in deionized water, is configured to the 1g/L-100g/L aqueous solution, will under conditions of 50-80 DEG C The 1g/L-100g/L trivalent iron salt aqueous solution is slowly dropped into silk protein aqueous solution, is stirred, wherein the silk-fibroin Mass ratio with trivalent iron salt is 1:1-10:1, it is molten as 1-5wt% calcium chloride that concentration is added dropwise using 30 drops/min speed Liquid, regulation pH value to 10-12, after 60 DEG C are at the uniform velocity stirred 1h, the sodium metaperiodate being slowly added in step 2 is modified salix cellulose, After ultrasonic mixing is uniform, pour into mould, be put into 1min in liquid nitrogen, be placed in pre-freeze 6h in -20 DEG C of refrigerators after taking-up, -80 DEG C 6h is freezed in Thermo ultra low temperature freezers, 48h in freeze dryer is then placed in and obtains magnetic porous composite material；Step 4：Configuration concentration 0.1-100g/L graphene oxide water solution, ultrasonic 1h will be magnetic porous multiple in step 3 Condensation material is immersed in 10-120min in graphene oxide solution, bath raio 1:50, after being cleaned repeatedly with ethanol and deionized water, very Sky is dried；Step 5：After the dipping of repeat step four-drying course 1-10 times, it is placed in reductant solution and is reduced, use ethanol Cleaned repeatedly with deionized water, graphene/silk/salix monogolica nano composite material is obtained after vacuum drying.
- 2. a kind of preparation method of graphene/silk/salix monogolica nano composite material according to claim 1, its feature exist In the silk-fibroin is that silk is made after degumming, dissolving, dialysis, purification.
- 3. a kind of preparation method of graphene/silk/salix monogolica nano composite material according to claim 1, its feature exist In the trivalent iron salt is the one or more in iron chloride, ferric sulfate, ferric nitrate.
- 4. a kind of preparation method of graphene/silk/salix monogolica nano composite material according to claim 1, its feature exist In the mass ratio of the calcium chloride and silk-fibroin is 1:10-1:50.
- 5. a kind of preparation method of graphene/silk/salix monogolica nano composite material according to claim 1, its feature exist In the mass ratio of the modified salix cellulose and silk-fibroin is 1:10-10:1.
- 6. a kind of preparation method of graphene/silk/salix monogolica nano composite material according to claim 1, its feature exist In the reducing agent is the one or more in hydrazine hydrate, sodium borohydride, sodium citrate, vitamin C, hydroiodic acid, Tea Polyphenols.
- A kind of 7. graphene/silk/salix monogolica nano composite material obtained by claim 1 preparation method.
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| CN104479174A (en) * | 2014-12-14 | 2015-04-01 | 苏州大学 | Cellulose-based magnetic aerogel material and preparation method thereof |
| CN106835367A (en) * | 2017-02-23 | 2017-06-13 | 东北师范大学 | A kind of cross-linked polysaccharides fiber and preparation method thereof |
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2017
- 2017-09-17 CN CN201710836586.9A patent/CN107556761A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103572395A (en) * | 2013-11-14 | 2014-02-12 | 东华大学 | Strengthened toughened regenerated silk fibers and preparation method thereof |
| CN104264259A (en) * | 2014-10-15 | 2015-01-07 | 钱景 | Graphene and salix psammophila regenerated cellulose blended fiber and preparation method thereof |
| CN104479174A (en) * | 2014-12-14 | 2015-04-01 | 苏州大学 | Cellulose-based magnetic aerogel material and preparation method thereof |
| CN106835367A (en) * | 2017-02-23 | 2017-06-13 | 东北师范大学 | A kind of cross-linked polysaccharides fiber and preparation method thereof |
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Application publication date: 20180109 |