CN110295401A - A kind of preparation method of pure chitosan superfine fibre - Google Patents
A kind of preparation method of pure chitosan superfine fibre Download PDFInfo
- Publication number
- CN110295401A CN110295401A CN201910612026.4A CN201910612026A CN110295401A CN 110295401 A CN110295401 A CN 110295401A CN 201910612026 A CN201910612026 A CN 201910612026A CN 110295401 A CN110295401 A CN 110295401A
- Authority
- CN
- China
- Prior art keywords
- solution
- superfine fibre
- pure chitosan
- spinning
- chitosan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of preparation methods of pure chitosan superfine fibre, 1- ethyl-3-methylimidazole acetate and N are dissolved chitosan in first, N '-dimethyl formamide (or N, N '-dimethyl acetamide) combination complex solvent in be prepared into spinning solution, then high-voltage electrostatic spinning, low temperature solidification, drying and processing are passed sequentially through to get pure chitosan superfine fibre.The present invention utilizes 1- ethyl-3-methylimidazole acetate and N, N '-dimethyl formamide (or N, N '-dimethyl acetamide) complex solvent dissolution chitosan, organic solvent N, N '-dimethyl formamide (or N, N '-dimethyl acetamide) plays the role of adjusting spinning fluid viscosity and dissolves chitosan.Used solvent green, environmental protection, the spinning solution performance prepared is stable, spinning properties are excellent.Without adding any auxiliary agent, the present invention is up to a kind of pure chitosan superfine fibre.
Description
Technical field
The present invention relates to electrospun fibers field of material technology more particularly to a kind of pure chitosan superfine fibres
Preparation method.
Background technique
Chitin of the natural polymer biological material chitosan in the albumen such as fish and shrimp marine product shell, silkworm chrysalis
Deacetylated product, it is resourceful, environmentally protective.Chitosan have many advantages, such as it is renewable, nontoxic, degradable, be nature
In be only second to the second largest living resources of cellulose, solution is the polysaccharose substance in alkalinity.It has bio-compatible simultaneously
Property, antibiotic property, the active group of carrying makes it possess preferable reactivity, is widely used in the necks such as medical treatment, health, absorption
Domain.However the polysaccharide molecule of the chitosan as natural polymer, since at its, intermolecular there are a large amount of hydrogen bonds with intramolecular
Make its performance and stable structure, but also results in it and be difficult to be separately dissolved in normal conventional solvent.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of pure chitosan superfine fibre, to solve to lack in the prior art
Make the green and environment-friendly solvent of chitosan high-efficiency dissolution, and is prepared using ionic liquid and organic solvent combining high-voltage electrostatic spinning
The problem of the technology shortage of pure chitosan superfine fibre.
The present invention the following steps are included:
(1) it is dissolved chitosan under the conditions of certain temperature in 1- ethyl-3-methylimidazole acetate ionic liquid, until
Clear homogeneous shape solution continues to add a certain amount of N into solution, N '-dimethyl formamide solution or N, N '-dimethyl acetyl
Amine aqueous solution, magnetic agitation to abundant dissolution, solution are transparent liquid to get pure chitosan spinning solution.
(2) high-voltage electrostatic spinning method is used, under certain condition by the obtained pure chitosan spinning solution of step (1),
By high-voltage electrostatic spinning shaping fiber shape up to pre-setting pure chitosan superfine fibre.
(3) the pre-setting pure chitosan superfine fibre in step (2) is solidified under certain condition and removes ionic liquid, dries
Dry pure chitosan superfine fibre to obtain the final product.
A kind of preparation method of pure chitosan superfine fibre as described above, wherein preferably, in the step (1)
The solution temperature that chitosan is dissolved in 1- ethyl-3-methylimidazole Acetate Solution is 50 DEG C~100 DEG C, the time be 1~
5h, remember by quality, the concentration of chitosan is 5~10%;Remember by quality, N, N '-dimethyl formamide solution or N, N '-diformazan
The amount of yl acetamide solution is 1~5 times of 1- ethyl-3-methylimidazole acetate, and under room temperature, magnetic agitation 1~5 is small
When, obtain the pure chitosan spinning solution.
A kind of preparation method of pure chitosan superfine fibre as described above, wherein preferably, in the step (2)
Static Spinning voltage is 20~30kv, and it is 10~20cm that fiber, which receives distance, and spinning speed is 0.5~2ml/h, and spinning temperature is
30~60 DEG C, obtain the pre-setting pure chitosan superfine fibre.
A kind of preparation method of pure chitosan superfine fibre as described above, wherein preferably, in the step (3)
The selected coagulating bath of solidification is dehydrated alcohol, setting temperature is 1~10 DEG C, 5~10h of time, drying temperature are 60~80 DEG C, is obtained
To the pure chitosan superfine fibre.Compared with prior art, the present invention has the advantage that: chitosan is dissolved in acid 1- second
In base -3- methylimidazole acetate ionic liquid, polysaccharide molecule palliating degradation degree is low, low energy consumption for course of dissolution, chitosan solution
Spinning property is excellent.
Detailed description of the invention
Fig. 1 is pure chitosan superfine fibre preparation flow figure of the invention.
Fig. 2 is the structure chart that the present invention is the pure chitosan superfine fibre that embodiment 1 mentions.
Specific embodiment
The embodiments described below with reference to the accompanying drawings are exemplary, for explaining only the invention, and cannot be construed to
Limitation of the present invention.The present invention dissolves chitosan in 1- second according to Fig. 1 preparation process flow under the conditions of certain temperature
In base -3- methylimidazole acetate ionic liquid, which can be with shell in the cation in acid while ionic liquid
The anion bindings such as the hydroxyl in glycan molecule, anion can be combined with the cation of the polysaccharide in chitosan molecule, be reached
To hydrogen bond action strong between molecule in chitosan molecule is destroyed, to achieve the purpose that dissolve chitosan.Due to ionic liquid
Body dissolves chitosan, and viscosity is larger later and solution does not have volatility, therefore can not be used to continue electrostatic spinning.Thus after
Continue and add a certain amount of N into solution, N '-dimethyl formamide solution or N, N '-dimethyl acetamide solution adjust viscosity, directly
Reach spinnable viscosity to solution, magnetic agitation to abundant dissolution, solution is transparent liquid, obtains pure chitosan spinning solution.Again
Using high-voltage electrostatic spinning method, under certain condition by pure chitosan spinning solution, by high-voltage electrostatic spinning shaping fiber shape,
Obtain pre-setting pure chitosan superfine fibre.It is so retained in the chitin fiber of pre-setting because ionic liquid is appointed, it is last
It needs to remove ionic liquid, pure chitosan superfine fibre obtained by drying under low temperature, coagulation bath condition.
Embodiment 1
The preparation of pure chitosan spinning solution: weighing 6g chitosan, be added to the 1- ethyl-3-methylimidazole acetate of 100g from
It in sub- liquid, is dissolved at 80 DEG C, continues the N for adding 200g into solution, N '-diformazan to clear homogeneous shape solution within dissolution 4 hours
Base formamide solution or N, N '-dimethyl acetamide solution, magnetic agitation 2 hours, solution are transparent liquid under room temperature,
Obtain pure chitosan spinning solution.
(2) high-voltage electrostatic spinning method is used, the obtained pure chitosan spinning solution of step (1) is packed into high-pressure electrostatic and is spun
In the matched micro propulsion pump of silk, the syringe needle with electrostatic high-pressure is flowed to by pipeline spinning solution, is with aluminium foil below syringe needle
Tunica fibrosa receiver board, setting Static Spinning voltage 25kv, fiber receive distance 15cm, spinning speed 1mL/h, spinning temperature 40
DEG C, obtain pre-setting pure chitosan superfine fibre.
(3) by the pre-setting pure chitosan superfine fibre in step (2) in dehydrated alcohol coagulating bath, 4 DEG C of conditions of temperature
Lower processing 7 hours, 70 DEG C of drying, obtains pure chitosan superfine fibre.
Fig. 2 is the structure chart of pure chitosan superfine fibre.It can be seen from the figure that pure chitosan superfine fibre has adhesion shape
In the presence of.This is because ionic liquid does not have volatility in chitosan solution, the conductive fiber for carrying ionic liquid is caused to exist
Electrostatic field stress drawing-off is inconsistent, and the obvolvent between fiber is caused to tangle state difference.Simultaneously because appointing in predetermined fiber type has
Ionic liquid exists, and when last solidification removes ionic liquid, fiber will appear diffusion, dispersion.
Embodiment 2
The preparation of pure chitosan spinning solution: weighing 5g chitosan, be added to the 1- ethyl-3-methylimidazole acetate of 100g from
It in sub- liquid, is dissolved at 70 DEG C, continues the N for adding 300g into solution, N '-diformazan to clear homogeneous shape solution within dissolution 2 hours
Base formamide solution or N, N '-dimethyl acetamide solution, magnetic agitation 2 hours, solution are transparent liquid under room temperature,
Obtain pure chitosan spinning solution.
(2) high-voltage electrostatic spinning method is used, the obtained pure chitosan spinning solution of step (1) is packed into high-pressure electrostatic and is spun
In the matched micro propulsion pump of silk, the syringe needle with electrostatic high-pressure is flowed to by pipeline spinning solution, is with aluminium foil below syringe needle
Tunica fibrosa receiver board, setting Static Spinning voltage 22kv, fiber receive distance 11cm, spinning speed 0.5mL/h, spinning temperature 50
DEG C, obtain pre-setting pure chitosan superfine fibre.
(3) by the pre-setting pure chitosan superfine fibre in step (2) in dehydrated alcohol coagulating bath, 7 DEG C of conditions of temperature
Lower processing 8 hours, 65 DEG C of drying, obtains pure chitosan superfine fibre.
Embodiment 3
The preparation of pure chitosan spinning solution: weighing 8g chitosan, be added to the 1- ethyl-3-methylimidazole acetate of 100g from
It in sub- liquid, is dissolved at 90 DEG C, continues the N for adding 400g into solution, N '-diformazan to clear homogeneous shape solution within dissolution 5 hours
Base formamide solution or N, N '-dimethyl acetamide solution, magnetic agitation 2 hours, solution are transparent liquid under room temperature,
Obtain pure chitosan spinning solution.
(2) high-voltage electrostatic spinning method is used, the obtained pure chitosan spinning solution of step (1) is packed into high-pressure electrostatic and is spun
In the matched micro propulsion pump of silk, the syringe needle with electrostatic high-pressure is flowed to by pipeline spinning solution, is with aluminium foil below syringe needle
Tunica fibrosa receiver board, setting Static Spinning voltage 30kv, fiber receive distance 19cm, spinning speed 2mL/h, spinning temperature 55
DEG C, obtain pre-setting pure chitosan superfine fibre.
(3) by the pre-setting pure chitosan superfine fibre in step (2) in dehydrated alcohol coagulating bath, 2 DEG C of conditions of temperature
Lower processing 6 hours, 80 DEG C of drying, obtains pure chitosan superfine fibre.
Structure, feature and effect of the invention, the above institute are described in detail based on the embodiments shown in the drawings
Only presently preferred embodiments of the present invention is stated, but the present invention does not limit the scope of implementation as shown in the drawings, it is all according to structure of the invention
Think made change or equivalent example modified to equivalent change, when not going beyond the spirit of the description and the drawings,
It should all be within the scope of the present invention.
Claims (4)
1. a kind of preparation method of pure chitosan superfine fibre, which comprises the following steps:
(1) it is dissolved chitosan under the conditions of certain temperature in 1- ethyl-3-methylimidazole acetate ionic liquid, until transparent
Uniform shape solution, continues to add a certain amount of N into solution, N '-dimethyl formamide solution or N, N '-dimethyl acetamide is molten
Liquid, magnetic agitation to abundant dissolution, solution are transparent liquid to get pure chitosan spinning solution.
(2) under certain condition by the obtained pure chitosan spinning solution of step (1) passed through using high-voltage electrostatic spinning method
High-voltage electrostatic spinning shaping fiber shape is up to pre-setting pure chitosan superfine fibre.
(3) the pre-setting pure chitosan superfine fibre in step (2) is solidified to remove ionic liquid, dry under certain condition and is
Obtain pure chitosan superfine fibre.
2. the preparation method of pure chitosan superfine fibre according to claim 1, it is characterised in that: shell is poly- in step (1)
The solution temperature that sugar is dissolved in 1- ethyl-3-methylimidazole Acetate Solution is 50 DEG C~100 DEG C, the time is 1~5h, by matter
Amount note, the concentration of chitosan are 5~10%;Remember by quality, N, N '-dimethyl formamide solution or N, N '-dimethyl acetamide
The amount of solution is 1~5 times of 1- ethyl-3-methylimidazole acetate, and under room temperature, 1~5h of magnetic agitation is obtained described pure
Chitosan spinning solution.
3. the preparation method of pure chitosan superfine fibre according to claim 1, it is characterised in that: electrostatic in step (2)
Spinning voltage is 20~30kv, and it is 10~20cm that fiber, which receives distance, and spinning speed is 0.5~2mL/h, and spinning temperature is 30~60
DEG C, obtain the pre-setting pure chitosan superfine fibre.
4. the preparation method of pure chitosan superfine fibre according to claim 1, it is characterised in that: solidification in step (3)
Selected coagulating bath is dehydrated alcohol, setting temperature is 1~10 DEG C, 5~10h of time, drying temperature are 60~80 DEG C, obtains institute
State pure chitosan superfine fibre.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910612026.4A CN110295401A (en) | 2019-07-08 | 2019-07-08 | A kind of preparation method of pure chitosan superfine fibre |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910612026.4A CN110295401A (en) | 2019-07-08 | 2019-07-08 | A kind of preparation method of pure chitosan superfine fibre |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110295401A true CN110295401A (en) | 2019-10-01 |
Family
ID=68030688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910612026.4A Pending CN110295401A (en) | 2019-07-08 | 2019-07-08 | A kind of preparation method of pure chitosan superfine fibre |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110295401A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113235187A (en) * | 2021-04-22 | 2021-08-10 | 常州大学 | Hyaluronic acid electrostatic spinning fiber containing polyion liquid and preparation method thereof |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101172164A (en) * | 2006-11-03 | 2008-05-07 | 中国科学院化学研究所 | Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same |
CN101507661A (en) * | 2009-03-10 | 2009-08-19 | 广州迈普再生医学科技有限公司 | Nano artificial dura mater with multi functional-layers and preparation method thereof |
CN101550610A (en) * | 2009-04-29 | 2009-10-07 | 青岛科技大学 | Preparation method of chitosan fiber |
CN101564914A (en) * | 2009-05-27 | 2009-10-28 | 东华大学 | Preparation method of nanometer cobweb/ nanometer fiber composite protective material |
US20090286078A1 (en) * | 2008-05-19 | 2009-11-19 | Industry-University Cooperation Foundation, Hanyang University | Polyimides dope composition, preparation method of hollow fiber using the same and hollow fiber prepared therefrom |
CN101586256A (en) * | 2009-07-06 | 2009-11-25 | 江苏泰灵生物科技有限公司 | Preparation of porosity electrospun fiber |
CN101724919A (en) * | 2009-08-13 | 2010-06-09 | 上海大学 | Device and method for preparing oriented polysulfonamide superfine fiber by using magnetized electrostatic spinning method |
CN102344685A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
CN102787447A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院化学研究所 | Shape memory material with fiber structure and preparation method of shape memory material |
CN102936762A (en) * | 2012-10-22 | 2013-02-20 | 中国纺织科学研究院 | Preparation method of chitosan/cellulose homogeneous spinning solution |
CN103409849A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Method for preparing chitosan hollow fiber membrane through treating composite ionic liquid as solvent |
CN106480518A (en) * | 2016-09-21 | 2017-03-08 | 华南理工大学 | A kind of electrostatic spinning collection device and the preparation method of gradient orientations structure nano fiber |
CN107354532A (en) * | 2017-06-28 | 2017-11-17 | 滁州市三和纤维制造有限公司 | A kind of preparation method of polyurethane-modified Fanglun slurry cake |
CN109293951A (en) * | 2017-07-25 | 2019-02-01 | 中国科学院化学研究所 | A kind of homogeneous phase solution and its preparation method and application containing responsiveness fluorescence polysaccharide derivates |
-
2019
- 2019-07-08 CN CN201910612026.4A patent/CN110295401A/en active Pending
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101172164A (en) * | 2006-11-03 | 2008-05-07 | 中国科学院化学研究所 | Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same |
US20090286078A1 (en) * | 2008-05-19 | 2009-11-19 | Industry-University Cooperation Foundation, Hanyang University | Polyimides dope composition, preparation method of hollow fiber using the same and hollow fiber prepared therefrom |
CN101507661A (en) * | 2009-03-10 | 2009-08-19 | 广州迈普再生医学科技有限公司 | Nano artificial dura mater with multi functional-layers and preparation method thereof |
CN101550610A (en) * | 2009-04-29 | 2009-10-07 | 青岛科技大学 | Preparation method of chitosan fiber |
CN101564914A (en) * | 2009-05-27 | 2009-10-28 | 东华大学 | Preparation method of nanometer cobweb/ nanometer fiber composite protective material |
CN101586256A (en) * | 2009-07-06 | 2009-11-25 | 江苏泰灵生物科技有限公司 | Preparation of porosity electrospun fiber |
CN101724919A (en) * | 2009-08-13 | 2010-06-09 | 上海大学 | Device and method for preparing oriented polysulfonamide superfine fiber by using magnetized electrostatic spinning method |
CN102344685A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
CN102787447A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院化学研究所 | Shape memory material with fiber structure and preparation method of shape memory material |
CN102936762A (en) * | 2012-10-22 | 2013-02-20 | 中国纺织科学研究院 | Preparation method of chitosan/cellulose homogeneous spinning solution |
CN103409849A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Method for preparing chitosan hollow fiber membrane through treating composite ionic liquid as solvent |
CN106480518A (en) * | 2016-09-21 | 2017-03-08 | 华南理工大学 | A kind of electrostatic spinning collection device and the preparation method of gradient orientations structure nano fiber |
CN107354532A (en) * | 2017-06-28 | 2017-11-17 | 滁州市三和纤维制造有限公司 | A kind of preparation method of polyurethane-modified Fanglun slurry cake |
CN109293951A (en) * | 2017-07-25 | 2019-02-01 | 中国科学院化学研究所 | A kind of homogeneous phase solution and its preparation method and application containing responsiveness fluorescence polysaccharide derivates |
Non-Patent Citations (3)
Title |
---|
PRAKASH等: ""Ion-imprinted electrospun nanofibers of chitosan/1-butyl-3-methylimidazolium tetrafluoroborate for the dynamic expulsion of thorium (IV) ions from mimicked effluents"", 《ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH》 * |
杨俊杰等: ""壳聚糖的溶解行为及其纤维研究进展"", 《中国材料进展》 * |
段久芳等: "《天然高分子材料》", 31 March 2016, 华中科技大学出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113235187A (en) * | 2021-04-22 | 2021-08-10 | 常州大学 | Hyaluronic acid electrostatic spinning fiber containing polyion liquid and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103993380B (en) | A kind of preparation method of Chitosan Fiber With High Tenacity | |
CN104436285B (en) | A kind of regenerated silk fibroin gel mould and preparation method thereof | |
CN103060946B (en) | Blend fibers of alginate and sodium carboxymethyl cellulose and preparation method and application thereof | |
CN108977912B (en) | Preparation method of collagen fiber | |
CN100430535C (en) | Alginate/polyvinyl alcohol composite fiber and its preparing process | |
CN104711702B (en) | There is the collagen aggregation composite type medical fiber of antibacterial/bacteria resistance function | |
CN109537163B (en) | Chitosan/sodium alginate/polyvinyl alcohol polyelectrolyte nanofiber composite membrane and preparation method thereof | |
CN103993422B (en) | A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof | |
CN104005114B (en) | A kind of preparation method of wool keratin regenerated celulose fibre | |
CN103320886A (en) | Bionic regenerated silk fibroin filament fiber and preparation method thereof | |
CN106267309A (en) | A kind of alginate compound antiseptic dressing and preparation method thereof | |
CN113638078B (en) | Polyelectrolyte complex hydrogel fiber and preparation method thereof | |
CN104474914A (en) | Nano filtering membrane containing silk fibroin and preparation method thereof | |
CN107118361B (en) | Silk fibroin/carboxymethyl chitosan composite gel and preparation method thereof | |
CN109881294A (en) | A kind of ionic liquid method regenerated cellulose/animal ceratin composite fibre and preparation method thereof | |
CN107325303B (en) | Degumming-free silk fiber solution, preparation method and application thereof | |
CN110295401A (en) | A kind of preparation method of pure chitosan superfine fibre | |
CN103834046A (en) | Method for preparing natural cellulose containing zein mixture by using alcoholic solvent | |
KR101862855B1 (en) | Chitosan fiber ion bonded with AU and the manufacturing of the same | |
CN101368328B (en) | Preparation method for hydroxyethyl group chitosan fiber | |
CN107137782A (en) | A kind of preparation method of the composite regenerated fiber repair materials of acetic acid | |
CN107185050A (en) | A kind of preparation method of the composite regenerated fiber repair materials of milk protein | |
CN102560741A (en) | Chitosan and polyvinyl pyrrolidone (PVP) blended fiber and preparation method thereof | |
CN105920655B (en) | A kind of degradable compound operation suture | |
CN101372764A (en) | Preparation of regenerated cellulose/chitin composite material and prepared composite fiber |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191001 |
|
RJ01 | Rejection of invention patent application after publication |