CN105839294A - Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method - Google Patents
Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method Download PDFInfo
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- CN105839294A CN105839294A CN201610342954.XA CN201610342954A CN105839294A CN 105839294 A CN105839294 A CN 105839294A CN 201610342954 A CN201610342954 A CN 201610342954A CN 105839294 A CN105839294 A CN 105839294A
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- fibroin
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- ncc
- micro crystal
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
- D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
- D01C3/02—De-gumming silk
-
- 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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Animal Husbandry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a method for preparing a nanocrystalline cellulose-fibroin film by an electrostatic spinning method. According to the method, a proper amount of homemade NCC (nanocrystalline cellulose) is added into a fibroin solution, a thorough mixing is carried out, and then, the NCC-fibroin film is prepared by the electrostatic spinning method, and the change of mechanical properties of a fibroin film before/after adding the NCC is researched; the prepared NCC-fibroin film is subjected to soaking treatment by methanol, and the change of the mechanical properties of the fibroin film is researched. According to the method, the anthe electrostatic-spun film is safe and non-toxic, the process is simple, the production cost is low, and the mechanical properties and the surface property of the fibroin film can be improved.
Description
Technical field
The invention belongs to field of light industry technology, be specifically related to a kind of method preparing nano micro crystal cellulose-fibroin membrane by method of electrostatic spinning.
Background technology
Method of electrostatic spinning be a kind of high speed prepare nanofiber effective ways [Dong Xiaoying, Dong Xin. the preparation technology of Electrospun nano-fibers and application [J] thereof. synthetic fiber industry, 2009,32
(4): 48-51.], fibroin albumen has preferable mechanical property, controls biological degradability and biocompatibility [Zhang
X H, Baughman C B, Kaplan D L. In vitro evaluation of electrospun silk fibroin
Scaffolds for vascular cell growth [J].
Biomaterials 2008;29 (14): 2217-2227.], fibroin albumen superfine fibre can be prepared by method of electrostatic spinning.But, the fragility of the electrospun fibers film generally prepared by method of electrostatic spinning is relatively big, and mechanical property is the highest, and therefore its range of application is necessarily limited to.
Nano micro crystal cellulose (NCC), as a kind of novel nano-material renewable, degradable, can be prepared by degraded native cellulose or microcrystalline Cellulose etc..Relation due to raw material, NCC not only has the characteristic of nanoparticle, also keep the basic chemical structure of cellulose, more optimize the performance of cellulose, there is [the M. Paakko such as large specific surface area, superpower absorbability, preferable mechanical performance, hyperfine structure, high-crystallinity, high Young's modulus and relatively extensive chemical reactivity, M. Ankerfors, H.
Kosonen. Enzymatic hydrolysis combined with mechanical shearing and
high-pressure homogenization for nanoscale cellulose fibrils and strong
Gels [J]. Biomacromolecules, 2007,8 (6): 1934-1941] advantage.NCC replacing other materials or directly applies to different field, to optimize some performance of material or to produce new performance, this is researchers' focus of attention.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that the preparation method of a kind of nano micro crystal cellulose static spinning membrane, comprise the steps:
Step (1): mulberry silk is placed in Na2CO3Aqueous solution (0.05%w/w) boils, continues 30min, repeat this operation three times, for removing the sericin in silkworm silk, obtain fibroin；Preparation CaCl2: C2H5OH: H2O
The ternary mixed solvent of=1:2:8 (mol ratio), being placed in one by fibroin, arranging bath raio is 1:50, is placed at a temperature of 75 ± 1 DEG C and prepares silk fibroin solution, by this solution after bag filter dialysis, filtering, the spongiform regenerated silk fibroin of freeze-dried mechanism emptying aperture much.
Step (2): the mass fraction arranging electrostatic spinning liquid is 8%, adds a certain amount of NCC.The regenerated silk fibroin that weighing is calculated and NCC, it is placed in sample bottle, it is dissolved in hexafluoroisopropanol, agitated is sufficiently mixed after uniformly, NCC-spinning liquid is poured in syringe cylinder, fix, between needle point and collecting board, spinning distance is 12cm, and spinning voltage is 15kv, and spinning flow rate is 0.6ml/h, carrying out electrostatic spinning, the NCC-fibroin membrane finally prepared is placed in stand for standby use in vacuum desiccator.
Step (3): prepare 90% methanol aqueous solution, be placed in one process 10min by the NCC-fibroin membrane prepared, and takes out and is dried at room temperature for.
Na in said method, described in step (1)2CO3, belonging to salt, the sodium carbonate containing ten water of crystallization is clear crystal, and water of crystallization is unstable, and easy-weathering becomes white powder Na2CO3, for strong electrolyte, there is the general character and the heat stability of salt, soluble in water, its aqueous solution is alkalescence.
CaCl in said method, described in step (1)2, colourless cubic crystal body, white or canescence, have granular, honeycomb is block, spherical shape, irregular particle shape, powder.Odorless, mildly bitter flavor, cheap be easy to get.
C in said method, described in step (1)2H5OH, is a kind of colourless transparent liquid inflammable, volatile under room temperature, normal pressure, and its aqueous solution has the abnormal smells from the patient of aroma, and slightly stimulates.There is the pungent flavour of smells of wine and stimulation, micro-sweet.
In said method, the methanol described in step (3), is colourless to have the volatile liquid of alcohol smell.
First mulberry silk is placed in Na by the present invention2CO3In solution, the sericin removed in silkworm silk obtains fibroin.Secondly fibroin is placed in ternary mixed solvent, adds NCC, make NCC be combined with fibroin.Finally fibroin Static Spinning is made into film, improves mechanical property and the surface property of fibroin membrane to a certain extent.
Detailed description of the invention
The present invention suitably makes NCC by oneself by adding in silk fibroin solution, prepares NCC-fibroin membrane by method of electrostatic spinning after sufficiently mixing, the mechanical property change of fibroin membrane before and after research interpolation NCC；The NCC-fibroin membrane prepared is changed through methanol immersion treatment, the mechanical property of research fibroin membrane.
Nano micro crystal cellulose, can be as the good reinforcer of one owing to having intensity and rigidity well.Meanwhile, compare inorganic filler, natural reproducible, pollution-free, bio-intermiscibility, there is substantial amounts of activity hydroxy additionally, due to its surface, it is simple to modified, these advantages are all that inorganic filler is incomparable.Therefore the present invention improves the mechanical property of fibroin membrane by adding nano micro crystal cellulose.
Below in conjunction with embodiment, the present invention is described further, but the scope of protection of present invention is not limited to the scope that embodiment is expressed.Except as otherwise noted, embodiment mid score and percentage ratio are all in terms of dry weight.
Embodiment 1
Mulberry silk is placed in Na2CO3Aqueous solution (0.05%w/w) boils, continues 30min, repeat this operation three times, for removing the sericin in silkworm silk, obtain fibroin；Preparation CaCl2: C2H5OH: H2O
The ternary solvent of=1:2:8 (mol ratio), being placed in one by fibroin, arranging bath raio is 1:50, is placed at a temperature of 75 ± 1 DEG C and prepares silk fibroin solution, by this solution after bag filter dialysis, filtering, the spongiform regenerated silk fibroin of freeze-dried mechanism emptying aperture much.The mass fraction arranging spinning liquid is 8%, and the nano micro crystal cellulose mass fraction of interpolation is 1%.The fibroin albumen that weighing is calculated and NCC, it is placed in 20ml sample bottle, it is dissolved in hexafluoroisopropanol (HFIP), agitated is sufficiently mixed after uniformly, NCC-spinning liquid is poured in syringe cylinder, fix, between needle point and collecting board, spinning distance is 12cm, and spinning voltage is 15kv, and spinning flow rate is 0.6ml/h, carrying out electrostatic spinning, the NCC-fibroin membrane finally prepared is placed in stand for standby use in vacuum desiccator.Preparing 90% methanol aqueous solution, be placed in one process 10min by the NCC-fibroin membrane prepared, and takes out and is dried at room temperature for.After treatment, hot strength is increased to 9.0MPa by 3.6MPa, rises 5.4MPa, and hot strength ascensional range is 111%.Before methanol processes, fibroin membrane average thickness is 0.1068mm, and after process, fibroin membrane average thickness is 0.0447mm.The methanol that compares is not added with the fibroin membrane of NCC before and after processing for, the toughness of Composite Fibroin Mambrane is largely improved.
Embodiment 2
Mulberry silk is placed in Na2CO3Aqueous solution (0.05%w/w, mass percent concentration) boils, continues 30min, repeat this operation three times, for removing the sericin in silkworm silk, obtain fibroin；Preparation CaCl2: C2H5OH: H2O
The ternary solvent of=1:2:8 (mol ratio), being placed in one by fibroin, arranging bath raio is 1:50, is placed at a temperature of 75 ± 1 DEG C and prepares silk fibroin solution, by this solution after bag filter dialysis, filtering, the spongiform regenerated silk fibroin of freeze-dried mechanism emptying aperture much.The mass fraction arranging spinning liquid is 8%, and the nano micro crystal cellulose mass fraction of interpolation is 3%.The fibroin albumen that weighing is calculated and NCC, it is placed in 20ml sample bottle, it is dissolved in HFIP, agitated is sufficiently mixed after uniformly, NCC-spinning liquid is poured in syringe cylinder, fix, between needle point and collecting board, spinning distance is 12cm, and spinning voltage is 15kv, and spinning flow rate is 0.6ml/h, carrying out electrostatic spinning, the NCC-fibroin membrane finally prepared is placed in stand for standby use in vacuum desiccator.Preparing 90% methanol aqueous solution, be placed in one process 10min by the NCC-fibroin membrane prepared, and takes out and is dried at room temperature for.Before and after treated, the hot strength of 3%NCC-fibroin membrane is risen to 9.8MPa by 1.8MPa, adds 8.0MPa, and hot strength ascensional range is 444%.Untreated front fibroin membrane average thickness is 0.1370mm, and after process, fibroin membrane average thickness is 0.0328mm.
Embodiment 3
Mulberry silk is placed in Na2CO3Aqueous solution (0.05%w/w) boils, continues 30min, repeat this operation three times, for removing the sericin in silkworm silk, obtain fibroin；Preparation CaCl2: C2H5OH: H2O
The ternary solvent of=1:2:8 (mol ratio), being placed in one by fibroin, arranging bath raio is 1:50, is placed at a temperature of 75 ± 1 DEG C and prepares silk fibroin solution, by this solution after bag filter dialysis, filtering, the spongiform regenerated silk fibroin of freeze-dried mechanism emptying aperture much.The mass fraction arranging spinning liquid is 8%, and the nano micro crystal cellulose mass fraction of interpolation is 5%.The fibroin albumen that weighing is calculated and NCC, it is placed in 20ml sample bottle, it is dissolved in HFIP, agitated is sufficiently mixed after uniformly, NCC-spinning liquid is poured in syringe cylinder, fix, between needle point and collecting board, spinning distance is 12cm, and spinning voltage is 15kv, and spinning flow rate is 0.6ml/h, carrying out electrostatic spinning, the NCC-fibroin membrane finally prepared is placed in stand for standby use in vacuum desiccator.Preparing 90% methanol aqueous solution, be placed in one process 10min by the NCC-fibroin membrane prepared, and takes out and is dried at room temperature for.After treatment, the hot strength of 5%NCC-fibroin membrane is increased to 6.6MPa by 2.2MPa, rises 4.4MPa, and hot strength ascensional range is 220%.Untreated front fibroin membrane average thickness is 0.0838mm, and after process, fibroin membrane average thickness is 0.0500mm.
It is NCC that the present invention used electrostatic spinning film properties improves material.NCC, as a kind of novel nano-material renewable, degradable, can be prepared by degraded native cellulose or microcrystalline Cellulose etc..Nano micro crystal cellulose static spinning membrane prepared by the present invention reduces due to the random coil and alpha helical conformation making fibroin albumen through the process of methanol, makes structure become more stable；There is more β parallel construction so that structure becomes more stable, make fibroin water insoluble, thus there is good mechanical property and surface property.
Claims (1)
1. the method preparing nano micro crystal cellulose-fibroin membrane by method of electrostatic spinning, it is characterised in that comprise the steps:
Step (1): mulberry silk is placed in Na2CO3Aqueous solution boils, continues 30 minutes, repeat this operation three times, for removing the sericin in silkworm silk, obtain fibroin；Preparation CaCl2: C2H5OH: H2O
The ternary mixed solvent of=1:2:8, this ratio is mol ratio, fibroin is placed in ternary mixed solvent, arranging bath raio is 1:50, it is placed at a temperature of 75 ± 1 DEG C and prepares silk fibroin solution, by this solution after bag filter dialysis, filtering, the spongiform regenerated silk fibroin of freeze-dried mechanism emptying aperture much；
Step (2): the mass fraction arranging spinning liquid is 8%, adds nano micro crystal cellulose；The fibroin albumen that weighing is calculated and nano micro crystal cellulose, it is placed in sample bottle, it is dissolved in hexafluoroisopropanol, after agitated son is sufficiently mixed uniformly, nano micro crystal cellulose-spinning liquid is poured in syringe cylinder, fix, between needle point and collecting board, spinning distance is 12cm, and spinning voltage is 15kv, and spinning flow rate is 0.6ml/h, carrying out electrostatic spinning, the nano micro crystal cellulose-fibroin membrane finally prepared is placed in stand for standby use in vacuum desiccator；
Step (3): prepare 90% methanol aqueous solution, be placed in one process 10min by the nano micro crystal cellulose-fibroin membrane prepared, and takes out and is dried at room temperature for.
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| CN201610342954.XA CN105839294A (en) | 2016-05-23 | 2016-05-23 | Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107287687A (en) * | 2017-06-26 | 2017-10-24 | 苏州威尔德工贸有限公司 | A kind of manufacture method of deodorization silk composite fiber |
| CN107287689A (en) * | 2017-06-26 | 2017-10-24 | 苏州威尔德工贸有限公司 | A kind of preparation method of the composite silk fiber of high-flexibility |
| CN108360285A (en) * | 2018-01-19 | 2018-08-03 | 华南理工大学 | The preparation method for adulterating the silk paper of Cellulose nanocrystal palpus and its application in facial mask |
| CN110124043A (en) * | 2019-05-17 | 2019-08-16 | 南京望知星医药科技有限公司 | A kind of salbutamol sulfate and preparation method thereof |
| CN110215351A (en) * | 2019-06-06 | 2019-09-10 | 杭州贝高母婴用品有限公司 | A kind of soft, paper diaper of pro-skin and its production technology |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107287687A (en) * | 2017-06-26 | 2017-10-24 | 苏州威尔德工贸有限公司 | A kind of manufacture method of deodorization silk composite fiber |
| CN107287689A (en) * | 2017-06-26 | 2017-10-24 | 苏州威尔德工贸有限公司 | A kind of preparation method of the composite silk fiber of high-flexibility |
| CN108360285A (en) * | 2018-01-19 | 2018-08-03 | 华南理工大学 | The preparation method for adulterating the silk paper of Cellulose nanocrystal palpus and its application in facial mask |
| CN110124043A (en) * | 2019-05-17 | 2019-08-16 | 南京望知星医药科技有限公司 | A kind of salbutamol sulfate and preparation method thereof |
| CN110215351A (en) * | 2019-06-06 | 2019-09-10 | 杭州贝高母婴用品有限公司 | A kind of soft, paper diaper of pro-skin and its production technology |
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Application publication date: 20160810 |