CN108754660A - A kind of preparation method for the natural silk fiber that graphene is modified - Google Patents
A kind of preparation method for the natural silk fiber that graphene is modified Download PDFInfo
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- CN108754660A CN108754660A CN201810553565.0A CN201810553565A CN108754660A CN 108754660 A CN108754660 A CN 108754660A CN 201810553565 A CN201810553565 A CN 201810553565A CN 108754660 A CN108754660 A CN 108754660A
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- silk fiber
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- 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
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
- D01F4/02—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from fibroin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
- C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
Abstract
The present invention provides a kind of preparation method for the natural silk fiber that graphene is modified, and graphite powder is added in the 50-70% concentrated sulfuric acids；2-4h is stirred to react with rate 800-1000r/min at 80-120 DEG C of temperature, is filtered with miillpore filter, it is neutrality to be washed repeatedly to filtrate, then is dried in vacuo at a temperature of 50-60 DEG C, and graphene oxide is obtained；Pure silk fibroin solution is obtained by filtration in sodium carbonate liquor degumming, dialysis, purification of the silk fiber through 8-10%；Graphene oxide and pure silk fibroin solution is set to mix using high-pressure atomization technique, control pressure 20-30MPa, flow rate of liquid is with 120-180 drops/min, and temperature is 70-80 DEG C；After the completion of mixing 2-3h is ultrasonically treated in 90-100 DEG C；Using melt-spinning technology, extruded spinning, stretching can be obtained the natural silk fiber of graphene modification.
Description
Technical field
The present invention relates to silk fiber preparing technical fields, and in particular to the natural silk fiber that a kind of graphene is modified
Preparation method.
Background technology
Natural-fiber composite material has attracted considerable concern in composite material research institution and industrially recently.This
It is a series of potential advantages due to natural fiber, the especially potential advantage in terms of its environmental performance.Natural fiber is can
Regenerated resource, and even when their composite waste is incinerated, they also do not cause carbon dioxide to be discharged into only
In environment.Natural fiber is inherently biodegradable, this can be beneficial.Due to its relatively low density, to Mr. Yu
For a little fibers such as flax, hemp and mestha, obtain and the comparable high ratio mechanical performance of the performance of glass fibre.It is other
Advantage is potential low cost and the relatively low investment required when planting natural fiber.In addition, these fibers are typically
Abrasion smaller than glass or carbon fiber, such as lead to the lower abrasion in textile processing and cause possible lower because of fibre
Tie up occupational health risks caused by dust.
Silk is secretion silk liquid concretionary continuous fiber when matured silkworm cocoons, also referred to as " natural silk ".It is with wool one
Sample is that one of the animal origin that the mankind utilize earliest is divided into silkworm, tussah, cassava silkworm, wild silkworm, willow silkworm according to the difference of food
With giant silkworm etc..The strand being pumped from single silk cocoon is known as silk, it borrows silk gum bonding to coat by two single fibers.It will be several
The silk of silk cocoon is extracted out, and strand made of silk gum bonding package is borrowed, and is divided into mulberry silk (also referred to as raw silk) and tussah silk, is referred to as
Silk.The silk for removing silk gum, is called refining silk.The application of silk is although very extensive at present, but there are electrostatic, toughness not
The problems such as sufficient.
Invention content
The purpose of the present invention is being directed to silk fiber preparation process above shortcomings in the prior art, a kind of stone is provided
The preparation method for the natural silk fiber that black alkene is modified strengthens its toughness to improve the electric conductivity of natural silk fiber.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
A kind of preparation method for the natural silk fiber that graphene is modified, includes the following steps：
S1：Graphite powder is added in the 50-70% concentrated sulfuric acids, the two solid-to-liquid ratio is 1:8-12；With rate at 80-120 DEG C of temperature
800-1000r/min is stirred to react 2-4h, is filtered with miillpore filter, and it is neutrality to be washed repeatedly to filtrate, then in 50-60 DEG C of temperature
The lower vacuum drying of degree, obtains graphene oxide；
S2：Pure silk fibroin solution is obtained by filtration in sodium carbonate liquor degumming, dialysis, purification of the silk fiber through 8-10%；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 20-30MPa, and flow rate of liquid is with 120-180 drops/min, and temperature is 70-80 DEG C；It is super in 90-100 DEG C after the completion of mixing
Sonication 2-3h；
S4：Using melt-spinning technology, extruded spinning, stretching can be obtained the natural silk fiber of graphene modification.
Preferably, graphite powder is added in 55% concentrated sulfuric acid described in step S1, the two solid-to-liquid ratio is 1:10；In temperature 110
3.5h is stirred to react with rate 900r/min at DEG C.
Preferably, it is dried in vacuo at a temperature of 55 DEG C in step S1.
Preferably, in step S2 by silk fiber the sodium carbonate liquor degumming 40-60min through 8-10%.
Preferably, in high-pressure atomization technique described in step S3 control pressure be 26MPa, flow rate of liquid be with 150 drop/
Min, temperature are 75 DEG C.
Preferably, after the completion of being mixed in step S3 2.5h is ultrasonically treated in 95 DEG C.
Preferably, the control of temperature described in step S4 is at 60-70 DEG C, and humid control is in 40-50%.
Preferably, the temperature control is at 65 DEG C, and humid control is 45%.
Advantageous effect：
The preparation method for the natural silk fiber that a kind of graphene of the present invention is modified, prepares graphene oxide and essence respectively
The pure silk fibroin solution of causeization is mixed using high-pressure atomization technique by liquid reactions, and control atomization process is prepared uniformly
Modified silk fiber preform；The natural silk fiber of graphene modification is made through melt-spinning technology after.The natural silk
Filamentary conductive can have very big promotion with toughness.
Specific implementation mode
It being further illustrated the present invention below in conjunction with following embodiments, following embodiments are merely to illustrate the present invention, and
The unrestricted present invention.
Embodiment 1
S1：Graphite powder is added in 50% concentrated sulfuric acid, the two solid-to-liquid ratio is 1:8；It is stirred with rate 800r/min at 80 DEG C of temperature
2h is reacted, is filtered with miillpore filter, it is neutrality to be washed repeatedly to filtrate, then is dried in vacuo at a temperature of 50 DEG C, is aoxidized
Graphene；
S2：Pure silk fibroin solution is obtained by filtration through 8% sodium carbonate liquor degumming 40min, dialysis, purification in silk fiber；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 20MPa, and flow rate of liquid is with 120 drops/min, and temperature is 70 DEG C；After the completion of mixing 2h is ultrasonically treated in 90 DEG C；
S4：Using melt-spinning technology, temperature control is at 60 DEG C, and 40%, extruded spinning, stretching can be obtained humid control
The natural silk fiber that graphene is modified.
The conductivity of above-mentioned natural silk fiber is 0.19S/cm, folding 50000 times or more.
Embodiment 2
S1：Graphite powder is added in 70% concentrated sulfuric acid, the two solid-to-liquid ratio is 1:12；With rate 1000r/min at 120 DEG C of temperature
It is stirred to react 4h, is filtered with miillpore filter, it is neutrality to be washed repeatedly to filtrate, then is dried in vacuo at a temperature of 60 DEG C, is obtained
Graphene oxide；
S2：Pure silk fibroin solution is obtained by filtration through 10% sodium carbonate liquor degumming 60min, dialysis, purification in silk fiber；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 30MPa, and flow rate of liquid is with 180 drops/min, and temperature is 80 DEG C；After the completion of mixing 3h is ultrasonically treated in 100 DEG C；
S4：Using melt-spinning technology, temperature control is at 70 DEG C, and 50%, extruded spinning, stretching can be obtained humid control
The natural silk fiber that graphene is modified.
The conductivity of above-mentioned natural silk fiber is 0.21S/cm, folding 50000 times or more.
Embodiment 3
S1：Graphite powder is added in 55% concentrated sulfuric acid, the two solid-to-liquid ratio is 1:9；It is stirred with rate 850r/min at 90 DEG C of temperature
2.5h is reacted, is filtered with miillpore filter, it is neutrality to be washed repeatedly to filtrate, then is dried in vacuo at a temperature of 52 DEG C, and oxygen is obtained
Graphite alkene；
S2：Pure silk fibroin solution is obtained by filtration through 8% sodium carbonate liquor degumming 45min, dialysis, purification in silk fiber；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 23MPa, and flow rate of liquid is with 140 drops/min, and temperature is 72 DEG C；After the completion of mixing 2.5h is ultrasonically treated in 95 DEG C；
S4：Using melt-spinning technology, temperature control is at 63 DEG C, and 43%, extruded spinning, stretching can be obtained humid control
The natural silk fiber that graphene is modified.
The conductivity of above-mentioned natural silk fiber is 0.24S/cm, folding 50000 times or more.
Embodiment 4
S1：Graphite powder is added in 65% concentrated sulfuric acid, the two solid-to-liquid ratio is 1:11；It is stirred with rate 950r/min at 110 DEG C of temperature
Reaction 3.5h is mixed, is filtered with miillpore filter, it is neutrality to be washed repeatedly to filtrate, then is dried in vacuo at a temperature of 58 DEG C, is obtained
Graphene oxide；
S2：Pure silk fibroin solution is obtained by filtration through 10% sodium carbonate liquor degumming 55min, dialysis, purification in silk fiber；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 28MPa, and flow rate of liquid is with 160 drops/min, and temperature is 78 DEG C；After the completion of mixing 3h is ultrasonically treated in 100 DEG C；
S4：Using melt-spinning technology, temperature control is at 67 DEG C, and 45%, extruded spinning, stretching can be obtained humid control
The natural silk fiber that graphene is modified.
The conductivity of above-mentioned natural silk fiber is 0.27S/cm, folding 50000 times or more.
Embodiment 5
S1：Graphite powder is added in 55% concentrated sulfuric acid, the two solid-to-liquid ratio is 1:10；It is stirred with rate 900r/min at 110 DEG C of temperature
Reaction 3.5h is mixed, is filtered with miillpore filter, it is neutrality to be washed repeatedly to filtrate, then is dried in vacuo at a temperature of 55 DEG C, is obtained
Graphene oxide；
S2：Pure silk fibroin solution is obtained by filtration through 9% sodium carbonate liquor degumming 55min, dialysis, purification in silk fiber；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 26MPa, and flow rate of liquid is with 150 drops/min, and temperature is 75 DEG C；After the completion of mixing 2.5h is ultrasonically treated in 95 DEG C；
S4：Using melt-spinning technology, temperature control is at 65 DEG C, and 45%, extruded spinning, stretching can be obtained humid control
The natural silk fiber that graphene is modified.
The conductivity of above-mentioned natural silk fiber is 0.3S/cm, folding 50000 times or more.
The foregoing is merely the better embodiment of the present invention, protection scope of the present invention is not with the above embodiment
Limit, as long as those of ordinary skill in the art should all be included in power according to equivalent modification or variation made by disclosed content
In protection domain described in sharp claim.
Claims (8)
1. a kind of preparation method for the natural silk fiber that graphene is modified, which is characterized in that include the following steps：
S1：Graphite powder is added in the 50-70% concentrated sulfuric acids, the two solid-to-liquid ratio is 1:8-12；With rate at 80-120 DEG C of temperature
800-1000r/min is stirred to react 2-4h, is filtered with miillpore filter, and it is neutrality to be washed repeatedly to filtrate, then in 50-60 DEG C of temperature
The lower vacuum drying of degree, obtains graphene oxide；
S2：Pure silk fibroin solution is obtained by filtration in sodium carbonate liquor degumming, dialysis, purification of the silk fiber through 8-10%；
S3：Pure silk fibroin solution mixing, control described in graphene oxide and step S2 in step S1 are made using high-pressure atomization technique
Pressure is 20-30MPa, and flow rate of liquid is with 120-180 drops/min, and temperature is 70-80 DEG C；It is super in 90-100 DEG C after the completion of mixing
Sonication 2-3h；
S4：Using melt-spinning technology, extruded spinning, stretching can be obtained the natural silk fiber of graphene modification.
2. the preparation method for the natural silk fiber that a kind of graphene according to claim 1 is modified, which is characterized in that step
Graphite powder is added in 55% concentrated sulfuric acid described in rapid S1, the two solid-to-liquid ratio is 1:10；With rate 900r/ at 110 DEG C of temperature
Min is stirred to react 3.5h.
3. the preparation method for the natural silk fiber that a kind of graphene according to claim 1 is modified, which is characterized in that step
It is dried in vacuo at a temperature of 55 DEG C in rapid S1.
4. the preparation method for the natural silk fiber that a kind of graphene according to claim 1 is modified, which is characterized in that step
By sodium carbonate liquor degumming 40-60min of the silk fiber through 8-10% in rapid S2.
5. the preparation method for the natural silk fiber that a kind of graphene according to claim 1 is modified, which is characterized in that step
Control pressure is 26MPa in high-pressure atomization technique described in rapid S3, and flow rate of liquid is with 150 drops/min, and temperature is 75 DEG C.
6. the preparation method for the natural silk fiber that a kind of graphene according to claim 1 is modified, which is characterized in that step
After the completion of being mixed in rapid S3 2.5h is ultrasonically treated in 95 DEG C.
7. the preparation method for the natural silk fiber that a kind of graphene according to claim 1 is modified, which is characterized in that step
Temperature control is at 60-70 DEG C described in rapid S4, and humid control is in 40-50%.
8. the preparation method for the natural silk fiber that a kind of graphene according to claim 7 is modified, which is characterized in that institute
Temperature control is stated at 65 DEG C, humid control is 45%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110368532A (en) * | 2019-06-21 | 2019-10-25 | 淮阴工学院 | A kind of preparation method of conducting polymer base graphene complex stephanoporate bracket |
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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 |
| CN106906531A (en) * | 2017-02-21 | 2017-06-30 | 南通强生石墨烯科技有限公司 | The preparation method of Graphene fibroin protein functional fiber |
| KR20180012095A (en) * | 2016-07-26 | 2018-02-05 | 주식회사 에스제이피일렉 | Methode of manufacturing conductive fiber |
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2018
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Patent Citations (4)
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| CN103173882A (en) * | 2013-04-11 | 2013-06-26 | 大连海事大学 | Method for preparing graphene/ silk composite fiber |
| CN103572395A (en) * | 2013-11-14 | 2014-02-12 | 东华大学 | Strengthened toughened regenerated silk fibers and preparation method thereof |
| KR20180012095A (en) * | 2016-07-26 | 2018-02-05 | 주식회사 에스제이피일렉 | Methode of manufacturing conductive fiber |
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| CN110368532A (en) * | 2019-06-21 | 2019-10-25 | 淮阴工学院 | A kind of preparation method of conducting polymer base graphene complex stephanoporate bracket |
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Application publication date: 20181106 |