CN105780184B - A kind of method that fiber is made in carboxymethyl cellulose progress electrostatic spinning - Google Patents
A kind of method that fiber is made in carboxymethyl cellulose progress electrostatic spinning Download PDFInfo
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- CN105780184B CN105780184B CN201610342421.1A CN201610342421A CN105780184B CN 105780184 B CN105780184 B CN 105780184B CN 201610342421 A CN201610342421 A CN 201610342421A CN 105780184 B CN105780184 B CN 105780184B
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- cellulose
- electrostatic spinning
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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
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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
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
A kind of method that carboxymethyl cellulose progress electrostatic spinning is made into fiber, is related to electrostatic spinning technique field, the present invention is by carboxymethyl cellulose（CMC）Polyvinyl alcohol is added in aqueous phase system（PVA）Suspension liquid of carboxyl methyl cellulose after solution and acidolysis, effectively improves carboxymethyl cellulose（CMC）Spinnability, thus obtained nanofiber diameter is about 300nm, shows bright and clean, and continuity is good, even thickness, and fineness degree is scattered narrower.
Description
Technical field
The present invention relates to electrostatic spinning technique field, the more particularly to technology of Biodegradable nano material and electrostatic spinning
Field.
Background technology
Method of electrostatic spinning is a kind of technology of high-efficiency production of nano fiber, forms the high polymer or molten mass of non-newtonian fluid
In the presence of high-pressure electrostatic power is broken through, nanofiber is formed, the only non-newtonian fluid with instability could be carried out quiet
Electrospun, this is one of essential characteristic of this method.Not only can be by a variety of synthesis and natural polymer electrospinning into single Nanowire
Dimension, composite nano-fiber material, such as the application of the technology such as coaxial spinning, three axle spinning, multilayer intersection spinning can also be obtained,
The fast development of the technology is promoted.
Due to the good characteristic of nano-fiber material performance, in film filter, tissue engineering bracket, bioengineering, clinic
Medical science, super dependent sensor, lithium battery material and ultracapacitor etc. have huge researching value, however, can enter at present
The common polymer species of row electrostatic spinning is also relatively fewer, is concentrated mainly on polyvinyl alcohol (PVA), polyacrylonitrile (PAN), gathers
Vinylpyrrolidone (PVP) etc., and be always the difficulty in the field to the research of the electrostatic spinning of polysaccharose substance and natural polymer
Point, extremely limit the further development of electrostatic spinning research.
Cellulose and derivative are one of resources for most having scale prospect, have the incomparable research valency of other materials
Value, such material is by the extensive concern of scholar in terms of electrostatic spinning research.It is referred to as the carboxymethyl of " industrial monosodium glutamate "
Cellulose（CMC）Have the advantages of other materials is incomparable, its cost is low, easily it is water-soluble, environment-friendly, technique is simple, extensively
Applied to fields such as oil, coating, food, membrane material, ceramics, medicine, battery, aviation and wides.But due to its own knot
The reason for structure and performance, its suitable Electrospun approach are rarely reported always.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, the present invention proposes that one kind can be by carboxymethyl cellulose（CMC）
It is spun into the method for fiber.
The present invention comprises the following steps：
1）Microcrystalline cellulose and the concentrated sulfuric acid being mixed, the stirring reaction under the conditions of 45 DEG C, reaction adds distilled water after terminating,
Obtain turbid；
2）With turbid described in distilled water centrifuge washing, it is transferred in bag filter, is put into deionized water and dialyses, work as deionized water
PH value when reaching neutrality, obtain Cellulose nanocrystal suspension；
3）By carboxymethyl cellulose（CMC）And polyvinyl alcohol（PVA）It is dissolved in deionized water, obtains carboxymethyl cellulose
（CMC）With the mixed solution of polyvinyl alcohol (PVA), then mixed solution mixed with Cellulose nanocrystal suspension, magnetic agitation
After stand, obtain the electrostatic spinning solution of bubble removing；
4）Electrostatic spinning：By the electrostatic spinning solution through Static Spinning, fiber is obtained.
Step 1 of the present invention）The concentration of the middle concentrated sulfuric acid is the optium concentration obtained through overtesting, and 45 DEG C of acidolysis can ensure crystallite
Cellulose obtains sufficient acidolysis, such as uses higher temperature, cellulose can interior carbonization in a short time.And low temperature can consume more
The long reaction time, and Product size cannot be guaranteed it is homogeneous.
The present invention is by carboxymethyl cellulose（CMC）Polyvinyl alcohol is added in aqueous phase system（PVA）After solution and acidolysis
Suspension liquid of carboxyl methyl cellulose, effectively improve carboxymethyl cellulose（CMC）Spinnability, thus obtained nanofiber
Diameter is about 300nm, shows bright and clean, and continuity is good, even thickness, and fineness degree is scattered narrower.
Further, step 1 of the present invention）The degree of polymerization of middle microcrystalline cellulose is 210~240, the μ of diameter 10~20
M, 100~200 μm of length.
In addition, the step 1）In, the mixed volume ratio of the concentrated sulfuric acid and distilled water is 1: 1, microcrystalline cellulose and the concentrated sulfuric acid
Mixing ratio be 1g: 8~15 mL.If the too low situation that acidolysis can be caused insufficient of concentrated sulfuric acid concentration, excessive concentration are easily led
Cause cellulose carbonization.
The step 1）In, mixing speed is 200~600 r/min.If rotating speed is too low, will be unable to scattered cellulose makes it
Abundant acidolysis, if rotating speed is too high, it may appear that the bad phenomenon such as pole-climbing.
The step 2）In every time centrifugation 10min, centrifuge speed 9000rmp/min.Cellulose is disperseed with solvent swelling state
Yu Shuizhong, if rotating speed is too low, the insufficient cellulose of acidolysis can not be centrifuged, rotating speed reaches 9000 cans, rotating speed
It is too high to be not necessarily to.
Carboxymethyl cellulose in the electrostatic spinning solution for removing bubble removing（CMC）Quality accounting be 1.0%, polyethylene
Alcohol（PVA）Quality accounting be 2.0%, nanocrystalline cellulose（NCC）Quality accounting be 0.7%.Test result indicates that simple
Nanocrystalline cellulose（NCC）The addition of suspension can not improve CMC spinnability well, and fiber surface morphology is not clean, slightly
It is thin uneven, after adding appropriate PVA solution, CMC spinning window has effectively been widened, and also gained fibre diameter is about 300nm,
Any surface finish, continuity is good, even thickness, disperses narrower.
The step 4）In, during Static Spinning, the distance between the needle point and reception device of electrostatic spinning apparatus is 15cm, solution
Flow velocity is 0.85ml/h, voltage 18kV, and the fiber morphology obtained under the conditions of being somebody's turn to do is ideal.
Brief description of the drawings
Fig. 1 is the optical microscope photograph that embodiment 1 prepares gained fiber.
Fig. 2 is the optical microscope photograph that comparative example 1 prepares gained fiber.
Fig. 3 is the optical microscope photograph that comparative example 2 prepares gained fiber.
Fig. 4 is the stereoscan photograph that embodiment 1 prepares gained fiber.
Fig. 5 is the stereoscan photograph that comparative example 1 prepares gained fiber.
Fig. 6 is the stereoscan photograph that comparative example 2 prepares gained fiber.
Fig. 7 is the diameter distribution profile that embodiment 1 prepares gained fiber.
Fig. 8 is the diameter distribution profile that comparative example 2 prepares gained fiber.
Embodiment
The present invention other advantages and effect by following embodiment continuing on.
First, embodiment 1：
1st, 5g microcrystalline celluloses and 50mL concentration are mixed for the 64wt% concentrated sulfuric acid, under the conditions of 45 DEG C, is through speed
200~600 r/min are stirred reaction, and reaction adds appropriate distilled water after terminating, obtain turbid.
The microcrystalline cellulose degree of polymerization used is 210~240,10~20 μm of diameter, 100~200 μm of length.
2nd, with the above-mentioned turbid of distilled water centrifuge washing 3 to 5 times, 10min, centrifuge speed 9000rmp/min are centrifuged every time,
It is then combined with the liquid phase that centrifuging and taking obtains to be placed in bag filter, is put into deionized water and dialyses, the pH value of periodic detection deionized water,
When the pH value of deionized water reaches neutrality, the Cellulose nanocrystal suspension in bag filter is obtained.
Appropriate distilled water is added after measuring suspension quality concentration, obtains the Cellulose nanocrystal that mass concentration is 1.4wt%
Suspension.
3rd, by 0.4g carboxymethyl celluloses（CMC）With 0.8g polyvinyl alcohol（PVA）It is dissolved in 18.8g deionized waters, obtains
To 20g carboxymethyl celluloses（CMC）With the mixed solution of polyvinyl alcohol (PVA).
Above-mentioned mixed solution is mixed with the Cellulose nanocrystal suspension that 20g concentration is 1.4wt% again, after magnetic agitation
Stand, obtain the electrostatic spinning solution of bubble removing.
Through analysis point, in the electrostatic spinning solution of bubble removing is removed, carboxymethyl cellulose（CMC）Quality accounting be 1.0%,
Polyvinyl alcohol（PVA）Quality accounting be 2.0%, nanocrystalline cellulose（NCC）Quality accounting be 0.7%.
4th, by the electrostatic spinning solution through Static Spinning, the distance between the needle point and reception device of electrostatic spinning apparatus is
15cm, solution flow rate 0.85ml/h, voltage 18kV, obtain fiber.
2nd, comparative example 1：
1st, by 0.2g carboxymethyl celluloses（CMC）It is dissolved in 19.8g deionized waters, obtains 20g carboxymethyl celluloses
（CMC）Solution.
Through analysis point, in the electrostatic spinning solution of bubble removing is removed, carboxymethyl cellulose（CMC）Quality accounting be 1.0%.
2nd, by carboxymethyl cellulose（CMC）Solution through Static Spinning, between the needle point and reception device of electrostatic spinning apparatus away from
From for 15cm, solution flow rate 0.85ml/h, voltage 18kV, fiber is obtained.
3rd, comparative example 2：
1st, 5g microcrystalline celluloses and 50mL concentration are mixed for 64wt% sulfuric acid, the stirring reaction under the conditions of 45 DEG C, reaction
Appropriate distilled water is added after end, obtains turbid.
The microcrystalline cellulose degree of polymerization used is 210~240,10~20 μm of diameter, 100~200 μm of length.
2nd, with the above-mentioned turbid of distilled water centrifuge washing 3 to 5 times, 10min, centrifuge speed 9000rmp/min are centrifuged every time,
It is then combined with the liquid phase that centrifuging and taking obtains to be placed in bag filter, is put into deionized water and dialyses, the pH value of periodic detection deionized water,
When the pH value of deionized water reaches neutrality, the Cellulose nanocrystal suspension in bag filter is obtained.
Appropriate distilled water is added after measuring suspension quality concentration, obtains the Cellulose nanocrystal that mass concentration is 1.4wt%
Suspension.
3rd, by 0.4g carboxymethyl celluloses（CMC）It is dissolved in 19.6g deionized waters, obtains 20g carboxymethyl celluloses
（CMC）Solution.
Again by above-mentioned carboxymethyl cellulose（CMC）Solution mixes with the Cellulose nanocrystal suspension that 20g concentration is 1.4wt%
Close, stood after magnetic agitation, obtain the electrostatic spinning solution of bubble removing.
Through analysis point, in the electrostatic spinning solution of bubble removing is removed, carboxymethyl cellulose（CMC）Quality accounting be 1.0%,
Nanocrystalline cellulose（NCC）Quality accounting be 0.7%.
4th, by the electrostatic spinning solution through Static Spinning, the distance between the needle point and reception device of electrostatic spinning apparatus is
15cm, solution flow rate 0.85ml/h, voltage 18kV, obtain fiber.
3rd, analysis result：
Fig. 1,2,3 are respectively embodiment 1, comparative example 1, the optical microscope photograph of the preparation gained fiber of comparative example 2.Can
To find out, fiber continuity is good made from embodiment 1, and diameter is more uniform, and comparative example 1 is containing only CMC solution, the mostly liquid of formation
Drop, it is difficult to form continuous fiber, appropriate NCC is added in comparative example 2, continuous fiber can be formed, but pattern is not as good as implementation
Example 1.
Fig. 4,5,6 are embodiment 1, comparative example 1, the stereoscan photograph of the preparation gained fiber of comparative example 2 respectively.It can see
Go out embodiment 1 and prepare gained fiber to show bright and clean, continuity is good, even thickness, disperses narrower, and comparative example 1 is mostly drop, right
Ratio 2 can prepare continuous fiber, but fiber thickness differs, diameter wider distribution.
Fig. 7,8 are respectively embodiment 1, the diameter distribution profile of the preparation gained fiber of comparative example 2, it can be seen that although both are flat
Equal diameter is more or less the same, but the distribution that embodiment 1 prepares gained fiber is significantly narrower than comparative example 2.It is it can be seen that proposed by the invention
Method can effectively improve CMC electrospinning, and the concentration is the optimum formula of CMC spinning.
Claims (5)
- A kind of 1. method that fiber is made in carboxymethyl cellulose progress electrostatic spinning, it is characterised in that comprise the following steps：1）Microcrystalline cellulose and the concentrated sulfuric acid are mixed, the stirring reaction under the conditions of 45 DEG C, reaction adds distilled water after terminating, and obtains Turbid；The degree of polymerization of the microcrystalline cellulose is 210~240,10~20 μm of diameter, 100~200 μm of length；2）With turbid described in distilled water centrifuge washing, it is transferred in bag filter, is put into deionized water and dialyses, as the pH of deionized water When value reaches neutrality, Cellulose nanocrystal suspension is obtained；3）Carboxymethyl cellulose and polyvinyl alcohol are dissolved in deionized water, obtain the mixed of carboxymethyl cellulose and polyvinyl alcohol Solution is closed, then mixed solution is mixed with Cellulose nanocrystal suspension, is stood after magnetic agitation, obtains the electrostatic of bubble removing Spinning solution；The quality accounting of carboxymethyl cellulose is 1.0% in the electrostatic spinning solution for removing bubble removing, polyvinyl alcohol Quality accounting is 2.0%, and the quality accounting of nanocrystalline cellulose is 0.7%；4）By the electrostatic spinning solution through Static Spinning, fiber is obtained.
- 2. preparation method according to claim 1, it is characterised in that the step 1）In, the mixture of the concentrated sulfuric acid and distilled water For product than being 1: 1, the mixing ratio of microcrystalline cellulose and the concentrated sulfuric acid is 1g: 8~15 mL.
- 3. preparation method according to claim 1, it is characterised in that the step 1）In, mixing speed is 200~600 r/ min。
- 4. preparation method according to claim 1, it is characterised in that the step 2）Middle centrifuge speed 9000rmp/min.
- 5. preparation method according to claim 1, it is characterised in that the step 4）In, during Static Spinning, electrostatic spinning apparatus Needle point and reception device between distance be 15cm, solution flow rate is 0.85mL/h, voltage 18kV.
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| KR20180044743A (en) * | 2016-10-24 | 2018-05-03 | 삼성전자주식회사 | Separator, Electrochemical cell comprising separator, Method for preparing separator, and Non woven fabric |
| CN106929929B (en) * | 2017-03-21 | 2019-06-07 | 昆明理工大学 | A kind of preparation method of the cellulose spin dope for electrostatic spinning |
| CN107201563B (en) * | 2017-06-09 | 2019-07-12 | 上海交通大学 | A kind of preparation method of the colored fiber based on Cellulose nanocrystal |
| CN108286082A (en) * | 2018-03-08 | 2018-07-17 | 唐卫兵 | A kind of preparation method of efficiently moisture-proof multilayer alkyd resin nano-cellulose spinning solution |
| CN109674721A (en) * | 2019-01-31 | 2019-04-26 | 杭州恒邦实业有限公司 | A kind of preparation method of carboxymethyl cellulose fiber facial mask |
| CN113355315B (en) * | 2021-05-31 | 2023-11-03 | 扬州大学 | Preparation method of pullulan-animal esterase composite nanofiber |
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| CN102943318A (en) * | 2012-11-28 | 2013-02-27 | 苏州大学 | polyvinyl alcohol (PVA)/sodium carboxy methylated cellulose (Na-CMC) nanofiber, preparation method and application |
| CN103866487A (en) * | 2014-03-27 | 2014-06-18 | 同济大学 | Method for preparing NCC/CS/PVA composite nano-membrane |
| CN104532480A (en) * | 2014-12-09 | 2015-04-22 | 广州贝奥吉因生物科技有限公司 | Nanometer microcrystalline cellulose reinforcing polylactic acid glycolic acid electrospun membrane, preparation method thereof and application |
| CN105506858A (en) * | 2016-01-26 | 2016-04-20 | 东北林业大学 | Method for preparing cellulose-reinforced nano-composite fiber membrane by electrostatic spinning |
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- 2016-05-23 CN CN201610342421.1A patent/CN105780184B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102943318A (en) * | 2012-11-28 | 2013-02-27 | 苏州大学 | polyvinyl alcohol (PVA)/sodium carboxy methylated cellulose (Na-CMC) nanofiber, preparation method and application |
| CN103866487A (en) * | 2014-03-27 | 2014-06-18 | 同济大学 | Method for preparing NCC/CS/PVA composite nano-membrane |
| CN104532480A (en) * | 2014-12-09 | 2015-04-22 | 广州贝奥吉因生物科技有限公司 | Nanometer microcrystalline cellulose reinforcing polylactic acid glycolic acid electrospun membrane, preparation method thereof and application |
| CN105506858A (en) * | 2016-01-26 | 2016-04-20 | 东北林业大学 | Method for preparing cellulose-reinforced nano-composite fiber membrane by electrostatic spinning |
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