CN105386153B - The preparation method of ethyl cellulose micro-and nano fiber - Google Patents
The preparation method of ethyl cellulose micro-and nano fiber Download PDFInfo
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- CN105386153B CN105386153B CN201510823696.2A CN201510823696A CN105386153B CN 105386153 B CN105386153 B CN 105386153B CN 201510823696 A CN201510823696 A CN 201510823696A CN 105386153 B CN105386153 B CN 105386153B
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- ethyl cellulose
- micro
- nano fiber
- spinning
- polyethylene glycol
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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
- 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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The present invention relates to micro nanometer fiber material preparation field, it is desirable to provide a kind of preparation method of ethyl cellulose micro-and nano fiber.This method includes：Ethanol water is dissolved in after ethyl cellulose and polyethylene glycol oxide are mixed, stirs spinning solution is made at room temperature；Spinning solution is subjected to centrifugal spinning, collected using annular collection mode；Ethyl cellulose micro-and nano fiber is immersed in deionized water, soaks, rinse at normal temperatures, be put into vacuum drying chamber and dry after the completion of immersion, obtain product.Of the invention simple, cheap, efficient, processing step is few, and process stabilization is efficient.The raw material used are cheap and easy to get, widened application prospect and use range in fields such as weaving, filtering, biology, food and medical treatment.Selected nontoxic solvent, not only improves environmental protection, also increases the reliability that Ethyl Cellulose Fibers are applied in fields such as food, medical treatment, biologies.Batch for ethyl cellulose micro-and nano fiber prepares and large-scale production provides effective means.
Description
Technical field
The invention belongs to micro nanometer fiber material preparation field, and in particular to a kind of system of ethyl cellulose micro-and nano fiber
Preparation Method.
Background technology
Cellulose is one of renewable resource most abundant on the earth.According to statistics, annual caused plant in worldwide
Goods and materials source is up to 10,00000000000 tons.Cellulose can be synthesized by photosynthesis by water and carbon dioxide, and and can is by the Nature
Microorganism is degradable, has good biocompatibility, therefore it is a kind of renewable resource and environment-friendly material.Fiber
Element because its is renewable, it is degradable and environment-friendly the features such as, can be for preparing the cellulose products of multiple functions, can be with
Various cellulose derivatives are prepared by derivative reaction, can partly replace a performance such as petroleum resources, now oil
The problems such as source faces shortage of resources, price rises make it that cellulose and its derivates are non-as the potential use range of host material
Often extensively, the focus that countries in the world are competitively developed is turned into.At present, cellulose and its derivates be widely used to weaving, plastics,
The domain variability fast development such as papermaking, food, medicine, building, biology and military affairs, following cellulose and its derivates will be most possible
One of important source material as chemical.
Ethyl cellulose is the cellulose derivative of earliest industrialized production.The chemical stability of ethyl cellulose is very
It is good, it is resistant to various alkali, diluted acid, salting liquid；There is excellent stability to light, ultraviolet irradiation will not be allowed to change colour；Ethyl cellulose
Cellulose-based film and plastics have superior mechanical strength within the scope of very wide temperature；Because it has unique and excellent property
Can, thus it is widely used, main application has following aspect：As plastic basis material be used for inject or extrusion forming thin slice, film and
Coating layer material；Hot-melt coating, strippable coatings, gel lacquer, paint, spray painting；Polyvinyl chloride matt film additive, bond
Agent, modifying agent, synthesize high polymer material suspension polymerization dispersant；The field such as medicine and food.
Cellulose derivative such as HEC, CMC, MC, HPMC, EC etc. have more by the technology of electrospun nanofibers
Report, but laboratory research is only limited to, yield is too low.
Centrifugal spinning technology is as a kind of important method for preparing micro nanometer fiber, in terms of yield, its single-nozzle
Up to nearly thousand times compared with conventional electrostatic spinning；In terms of raw material selection, centrifugal spinning is no longer limited by material polarity.
It is existing centrifugation spin achievement in research in, spinning material mainly using synthetic high polymer such as PAN, PA6, PP, PBT,
PMMA, PVP and PEO etc., it is primarily due to, and synthetic high polymer strand is regular, unbranched or branching content is few, and
And relative molecular weight is high and narrow distribution range is suitable for spinning fibre, this also complies with the general requirement of fiber-forming polymer.However, day
Right macromolecule such as starch, cellulose etc. cause relative molecular weight distribution extensive because its source inherently has differences, and have
Branched-chain component is more on a little main chains or side base is huge, and this brings difficulty, i.e., simple fibre to the spinning of cellulose derivative
It is difficult spinning to tie up plain derivative solution.
In the report being currently known, such as article " Xiaohui Wu, Linge Wang, et al..Effect of
Solvent on Morphology of Electrospinning Ethyl Cellulose Fibers[J].Journal of
Applied Polymer Science,2005,97(3):1292-1297. " and " Bilal Ahmad, Simeon Stoyanov,
et al..Electrospinning of ethyl cellulose fibres with glass and steel
configurations[J].Food Research International,2013,54(2):1761-1772. " in, choose phase
Laboratory research is carried out to the ethyl cellulose medicine of the higher narrow distribution range of molecular weight, but the drug price after purifying is expensive
It is adapted only to laboratory research, production can not be promoted；As article " Audrey Frenot, Maria Walenius Henriksson,
et al..Electrospinning of Cellulose-Based Nanofibers[J].Journal of Applied
Polymer Science,2007,103:1473-1482. " in, studied using water miscible derivative, so produced
Fiber meet water dissolving, greatly limit its application；And for example " Um-i-Zahra, S., et al..Study of
sustained release drug-loaded nanofibers of cellulose acetate and ethyl
cellulose polymer blends prepared by electrospinning and their in-vitro drug
release profiles[J].Journal of Polymer Research,2014,21(12):602-613. " etc. some text
Zhang Zhong, majority prepare nanofiber using virose organic solvent ethyl cellulose dissolved, using poisonous organic solvent not
Potential safety hazard is only existed, also results in air or water pollution, is unfavorable for environmental protection, and these researchs are all to use electrostatic
Spin, the spinning efficiency using centrifugal spinning technology is significantly lower than on yield.
At present, the report for preparing ethyl cellulose micro-and nano fiber by centrifugal spinning technology not yet occurs.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided a kind of using nontoxic binary
The method that dicyandiamide solution quickly prepares ethyl cellulose micro-and nano fiber.For this method using ethyl cellulose as raw material, addition can be with
The polyethylene glycol oxide of spinnability is improved, using second alcohol and water as solvent, by centrifugal spinning technology, adjusts solvent and related spinning bar
Part parameter, it is successfully realized the quick preparation of ethyl cellulose micro-and nano fiber.
To solve technical problem, solution of the invention is：
A kind of preparation method of ethyl cellulose micro-and nano fiber is provided, comprised the following steps：
(1) centrifugal spinning prepares ethyl cellulose micro-and nano fiber
In mass ratio 10~20: 1 mixes ethyl cellulose and polyethylene glycol oxide, is then dissolved in the second that volume ratio is 7: 3
The in the mixed solvent of alcohol and water, 10 hours obtained spinning solutions are stirred at room temperature；In spinning solution, the concentration of ethyl cellulose for 10~
20% (w/v), the concentration of polyethylene glycol oxide is 1% (w/v)；
Spinning solution is injected into centrifugal spinning device, under conditions of 12 centimetres 3000 revs/min of rotating speed, reception of distance
Centrifugal spinning is carried out, ethyl cellulose micro-and nano fiber is collected using annular collection mode, it is 45 ± 5% to control ambient humidity；
(2) post-processing approach of ethyl cellulose micro-and nano fiber
Ethyl cellulose micro-and nano fiber is immersed in deionized water, soaked 96 hours at normal temperatures；It is every in immersion process
Taken out every 24 hours and repeat to rinse with deionized water, change deionized water used in immersion；By ethyl cellulose after the completion of immersion
Micro nanometer fiber is put into vacuum drying chamber, is dried 24 hours at 50 DEG C, obtains eliminating the ethyl of polyethylene glycol oxide composition
Cellulose micro-nano fiber product.
In the present invention, the viscosity of described ethyl cellulose is 18~330mPas, described polyethylene glycol oxide it is relative
Molecular weight ranges are 100,000~4,000,000.
In the present invention, the spinning device in the centrifugal spinning device is using dispensing needle head as spinning head.
In the present invention, a diameter of 500nm~10 μm for the ethyl cellulose micro-and nano fiber being prepared.Ethyl cellulose
The diameter of micro nanometer fiber changes and changed according to the needle diameter used, and it is smaller that syringe needle gets over fibre diameter.
The beneficial effects of the invention are as follows：
(1) the inventive method is simple to operate, and processing step is few, by centrifugal spinning technology, can obtain micro/nano level
Fiber, process stabilization is efficient, suitable for the large-scale production of ethyl cellulose, while is also applied for variety classes cellulose derivative
The spinning of thing.
(2) raw material used in the present invention are cheap and easy to get, and the fiber of preparation can be controlled between 500nm~10 μm,
Its application prospect and use range in fields such as weaving, filtering, biology, food and medical treatment is widened, further slow down makes
With the pressure of synthetic material, can also be played a role in improving in terms of environmental protection.
(3) solvent selected by is nontoxic ethanol water mixed solvent, not only improves environmental protection, also increases ethyl cellulose
The reliability that fiber is applied in fields such as food, medical treatment, biologies.
(4) this method is simple, cheap, efficient, is the batch preparation and large-scale production of ethyl cellulose micro-and nano fiber
Provide effective means.
Brief description of the drawings
Fig. 1 is the SEM figures (10000 times of amplification) of Ethyl Cellulose Fibers made from the embodiment of the present invention 1；
Fig. 2 is the SEM figures (1000 times of amplification) of Ethyl Cellulose Fibers made from the embodiment of the present invention 1；
Fig. 3 is the SEM figures (10000 times of amplification) of Ethyl Cellulose Fibers made from the embodiment of the present invention 2；
Fig. 4 is the SEM figures (1000 times of amplification) of Ethyl Cellulose Fibers made from the embodiment of the present invention 2；
Fig. 5 is the SEM figures (30000 times of amplification) of Ethyl Cellulose Fibers made from the embodiment of the present invention 3；
Fig. 6 is the SEM figures (5000 times of amplification) of Ethyl Cellulose Fibers made from the embodiment of the present invention 3.
Embodiment
With reference to specific embodiment, the invention will be further described.
Centrifugal spinning device used can use conventional centrifugal device for spinning in the present invention, and spinning device therein is using point plastic pin
Head is used as spinning head.Because belonging to prior art, the present invention repeats no more.
Embodiment 1：
By 1g ethyl celluloses and 0.1g polyethylene glycol oxides (10:1) 7mL ethanol and 3mL water (7 are dissolved in after mixing:3) mixed
In bonding solvent, ethyl cellulose concentration is 10% (w/v), and polyethylene glycol oxide concentration is 1% (w/v), is stirred 10 hours at room temperature
Spinning solution is made.Ethyl cellulose viscosity parameter used is 330mPas, and polyethylene glycol oxide relative molecular weight is 4,000,
000。
The spinning solution is injected into centrifugal spinning device, is 3000 revs/min in rotating speed, it is 12 centimetres to receive distance
Under conditions of carry out centrifugal spinning, select the syringe needle that specification is 25G to be used as spinning head, annular collection, ambient humidity is maintained at 45
± 5%.
Obtained fibrous material is immersed in deionized water, soaked 96 hours at normal temperatures, was taken out every 24 hours above-mentioned
Fibrous material is repeated to rinse with deionized water, and changes described immersion deionized water, and fibrous material finally is put into vacuum
Dried 24 hours at 50 DEG C in drying box, obtaining removal, adding ingredient --- the cellulose content of polyethylene glycol oxide approaches
Absolutely fiber, diameter range is at 4 μm~10 μm.
Embodiment 2：
By 1.5g ethyl celluloses and 0.1g polyethylene glycol oxides (15:1) 7mL ethanol and 3mL water (7 are dissolved in after mixing:3)
In the mixed solvent, ethyl cellulose concentration are 15% (w/v), and polyethylene glycol oxide concentration is 1% (w/v), and it is small to stir 10 at room temperature
When be made spinning solution.Ethyl cellulose viscosity parameter used is 270mPas, and polyethylene glycol oxide relative molecular weight is 2,000,
000。
The spinning solution is injected into centrifugal spinning device, is 3000 revs/min in rotating speed, it is 12 centimetres to receive distance
Under conditions of carry out centrifugal spinning, select the syringe needle that specification is 25G to be used as spinning head, annular collection, ambient humidity is maintained at 45
± 5%.
Obtained fibrous material is immersed in deionized water, soaked 96 hours at normal temperatures, was taken out every 24 hours above-mentioned
Fibrous material is repeated to rinse with deionized water, and changes described immersion deionized water, and fibrous material finally is put into vacuum
Dried 24 hours at 50 DEG C in drying box, obtaining removal, adding ingredient --- the cellulose content of polyethylene glycol oxide approaches
Absolutely fiber, diameter range is at 3 μm~8 μm.
Embodiment 3：
(20 after 1g ethyl celluloses and 0.05g polyethylene glycol oxides are mixed:1) it is dissolved in 3.5mL ethanol and 1.5mL water (7:
3) in the mixed solvent, ethyl cellulose concentration are 20% (w/v), and polyethylene glycol oxide concentration is 1% (w/v), is stirred at room temperature
10 hours obtained spinning solutions, ethyl cellulose viscosity parameter used are 18mPas, and polyethylene glycol oxide relative molecular weight is 1,
000,000。
The spinning solution is injected into centrifugal spinning device, is 3000 revs/min in rotating speed, it is 12 centimetres to receive distance
Under conditions of carry out centrifugal spinning, select the syringe needle that specification is 25G to be used as spinning head, annular collection, ambient humidity is maintained at 45
± 5%.
Obtained fibrous material is immersed in deionized water, soaked 96 hours at normal temperatures, was taken out every 24 hours above-mentioned
Fibrous material is repeated to rinse with deionized water, and changes described immersion deionized water, and fibrous material finally is put into vacuum
Dried 24 hours at 50 DEG C in drying box, obtaining removal, adding ingredient --- the cellulose content of polyethylene glycol oxide approaches
Absolutely fiber, diameter range is in 500nm~3 μm.
It is noted that above example is merely to illustrate the present invention, it is easy to those skilled in the art to further understand this
The technical concepts and features of invention, but the invention is not limited in any way.It should be pointed out that to those skilled in the art,
Without departing from the inventive concept of the premise, various changes or modification are made to the present invention, these equivalent form of values also belong to this
Invention appended claims limited range.
Claims (3)
1. a kind of preparation method of ethyl cellulose micro-and nano fiber, it is characterised in that comprise the following steps：
(1) centrifugal spinning prepares ethyl cellulose micro-and nano fiber
In mass ratio 10~20: 1 mixes ethyl cellulose and polyethylene glycol oxide, be then dissolved in ethanol that volume ratio is 7: 3 and
The in the mixed solvent of water, 10 hours obtained spinning solutions are stirred at room temperature；In spinning solution, the concentration of ethyl cellulose is 10~20%
(w/v), the concentration of polyethylene glycol oxide is 1% (w/v)；
Spinning solution is injected into centrifugal spinning device, carried out under conditions of 12 centimetres 3000 revs/min of rotating speed, reception of distance
Centrifugal spinning, ethyl cellulose micro-and nano fiber is collected using annular collection mode, it is 45 ± 5% to control ambient humidity；
(2) post-processing approach of ethyl cellulose micro-and nano fiber
Ethyl cellulose micro-and nano fiber is immersed in deionized water, soaked 96 hours at normal temperatures；Every 24 in immersion process
Hour is taken out and rinsed repeatedly with deionized water, changes deionized water used in immersion；By ethyl cellulose micro-nano after the completion of immersion
Rice fiber is put into vacuum drying chamber, is dried 24 hours at 50 DEG C, obtains eliminating the ethyl cellulose of polyethylene glycol oxide composition
Plain micro nanometer fiber product；
The viscosity of described ethyl cellulose is 18~330mPas, and the relative molecular weight scope of described polyethylene glycol oxide is
1,000,000~4,000,000.
2. according to the method for claim 1, it is characterised in that the spinning device in the centrifugal spinning device is using point plastic pin
Head is used as spinning head.
3. according to the method for claim 1, it is characterised in that the diameter for the ethyl cellulose micro-and nano fiber being prepared
For 500nm~10 μm.
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| CN108939154A (en) * | 2018-07-16 | 2018-12-07 | 武汉纺织大学 | A kind of preparation method of collagen protein composite fiber bracket |
| CN110344127A (en) * | 2019-06-23 | 2019-10-18 | 浙江理工大学 | A kind of centrifugal spinning preparation method of porous Kynoar/polyethylene glycol oxide micro/nano-fibre |
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