CN106380611B - A kind of preparation method of ethyl chitosan film - Google Patents
A kind of preparation method of ethyl chitosan film Download PDFInfo
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- CN106380611B CN106380611B CN201610765755.XA CN201610765755A CN106380611B CN 106380611 B CN106380611 B CN 106380611B CN 201610765755 A CN201610765755 A CN 201610765755A CN 106380611 B CN106380611 B CN 106380611B
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- Prior art keywords
- film
- ethyl
- chitosan
- ethyl chitosan
- constant temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0023—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/60—Materials for use in artificial skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a kind of preparation methods of ethyl chitosan film, self-control ethyl chitosan is dissolved in 1~5% glycine hydrochloride saline solution, it is completely dissolved the ethyl chitosan stoste that 1~5wt% of concentration is made, it is filtered through squeezing, discontinuous degassing, spin-coating on glass plate, 40 DEG C of constant humidity 50% of constant temperature are dry, 1~5h of soaked in absolute ethyl alcohol takes off film, water washing is distilled to neutrality, and the operation such as 40 DEG C of dryings of constant humidity 50% of constant temperature, obtain ethyl chitosan film, gained film with a thickness of 1.5~2 μm, breaking strength >=180MPa, elongation at break > 3.7%, initial modulus > 4.5GPa.The film can be used as anticoagulant material, bone renovating material, wound dressing etc..
Description
Technical field
The invention belongs to the preparation technical fields of membrane material, and in particular to a kind of preparation method of ethyl chitosan film, it should
Method not only extends the type of chitosan class film, at the same overcome solvent during current chitosan class film preparation it is volatile,
Seriously polluted, the disadvantages of three-protection design amount is larger.Specifically using the self-control ethyl chitosan of high molecular weight as raw material, with sweet ammonia
The aqueous solution of acid hydrochloride is solvent, prepares the preparation liquid of suitable concentration；Spin-coating is carried out using sol evenning machine, using immersion
The processes such as film, constant temperature and humidity drying are taken off, ethyl chitosan film is finally obtained.
Background technique
Chitin is a kind of high-molecular biologic matter resource, and it is dynamic to be widely present in the arthropods such as marine organisms shrimp, crab, software
In object and fungal cell, there is the title of tunicin.But the hydrogen bond structure in chitin molecule is complicated, leads to its dissolubility pole
Difference, therefore what is be most widely used at present is its deacetylated product chitosan.But amino largely exposed, makes it on chitosan
The positive charge quantity on surface increases, and is restricted its application range, such as is used as medical releasing film.Function is carried out to its amino
Change, such as introduces alkyl, its performance will be significantly improved, extend its application space.Invention person is in patent
It refers to alkalize to high molecular weight chitosan under microwave radiation in CN201010253792, destroy between chitosan molecule
The long-chain N- alkyl chitosan (C that degree of substitution is 40~70% has been made in hydrogen bond12-C16), inventor still uses this in this patent
One technique, ethyl is introduced into chitosan molecule, the ethyl chitosan of different degree of substitution is made, and using it as raw material, and second is made
Base enclosure glycan sugar film.Currently, being mostly the technique for continuing to use chitosan film about ethyl chitosan film preparation technique, according to existing pass
It is resulting in the patent (e.g., CN03118535.5, CN201410025894.X, CN201310492147.2) of chitosan film preparation
The mechanical strength of ethyl chitosan film is all very low, and therefore, how to improve filming technology technology is to prepare high-performance ethyl shell to gather
The critical issue of sugared film.
Summary of the invention
The invention reside in provide a kind of preparation method of ethyl chitosan film.
The present invention is implemented as follows:
Will self-control ethyl chitosan be dissolved in 1~5% glycine hydrochloride saline solution, be completely dissolved be made concentration 1~
The ethyl chitosan stoste of 5wt%, it is dry through 40 DEG C of spin-coating, constant temperature constant humidity 50% on extruding filtering, discontinuous degassing, glass plate
Dry, 1~5h of soaked in absolute ethyl alcohol takes off film, distillation water washing to neutrality, and the operation such as 40 DEG C of dryings of constant humidity 50% of constant temperature, obtains second
Base chitosan film, gained ethyl chitosan film with a thickness of 1.5~2 μm, breaking strength >=180MPa, elongation at break >
3.7%, initial modulus > 4.5GPa.
Wherein, ethyl chitosan viscosity≤180CPS (with acetate concentration be 1% when), degree of substitution 8-20%, moisture≤
7.0%, ash content≤0.6%.Under the above conditions, gained ethyl chitosan film with a thickness of 1.5~2 μm, breaking strength >=
180MPa, elongation at break > 3.7%, initial modulus > 4.5GPa.
Film build method of the present invention is spin-coating method.
The ethyl chitosan film that the present invention mentions overcomes the low disadvantage of intensity possessed by existing chitosan class film, together
The reduction of Shi Yinwei film thickness and surface cationic charge, anti-inflammatory, it is antibacterial, in terms of show more preferable effect,
Chitosan class film is expanded in the application in the fields such as bio-medical auxiliary material, health care.
The invention has the following advantages that
(1) the ethyl chitosan film that this patent method is produced, property nontoxic to the human body, it is non-stimulated, without allergy, can be by human body group
Degradation is knitted to absorb.
(2) breaking strength >=180MPa for the ethyl chitosan film that this patent method is produced, elongation at break > 3.7% should
Film can be used for the medicine such as anticoagulant material, bone renovating material, artificial skin, wound dressing, medicament carrier system, artificial biological film
Field.
Specific embodiment
It further illustrates with reference to embodiments, not limits range according to the present invention.
Embodiment 1:
The glycine hydrochloride saline solution 50g for preparing 1.5%, 0.75g ethyl chitosan (degree of substitution 8%) is completely dissolved
In above-mentioned solvent, the ethyl chitosan that concentration is 1.5% is made and is film-made stoste, through on extruding filtering, standing and defoaming, glass plate
40 DEG C of spin-coating, constant temperature constant humidity 50% are dry, ethanol solution impregnates 2.5h and takes off film, distillation water washing to neutrality, and permanent
The operations such as 40 DEG C of constant humidity 50% of temperature are dry, obtain transparent ethyl chitosan film, with a thickness of 1.52 μm, breaking strength
181MPa, elongation at break 3.97%, initial modulus 4.52GPa.
Embodiment 2:
The glycine hydrochloride saline solution 50g for preparing 2.0%, 1.25g ethyl chitosan (degree of substitution 12%) is completely molten
In the above-mentioned solvent of Xie Yu, the ethyl chitosan that concentration is 2.5% is made and is film-made stoste, through squeezing filtering, standing and defoaming, glass plate
40 DEG C of upper spin-coating, constant temperature constant humidity 50% are dry, ethanol solution impregnates 3.5h and takes off film, distillation water washing to neutrality, and
The operations such as 40 DEG C of constant humidity 50% of constant temperature are dry, obtain transparent ethyl chitosan film, with a thickness of 1.82 μm, breaking strength
187MPa, elongation at break 4.21%, initial modulus 4.77GPa.
Embodiment 3:
The glycine hydrochloride saline solution 50g for preparing 3.0%, 1.0g ethyl chitosan (degree of substitution 16%) is completely dissolved
In above-mentioned solvent, the ethyl chitosan that concentration is 2.0% is made and is film-made stoste, through on extruding filtering, standing and defoaming, glass plate
40 DEG C of spin-coating, constant temperature constant humidity 50% are dry, ethanol solution impregnates 3.0h and takes off film, distillation water washing to neutrality, and permanent
The operations such as 40 DEG C of constant humidity 50% of temperature are dry, obtain transparent ethyl chitosan film, with a thickness of 1.92 μm, breaking strength
192MPa, elongation at break 3.85%, initial modulus 4.65GPa.
Embodiment 4:
The glycine hydrochloride saline solution 50g for preparing 1.0%, 0.5g ethyl chitosan (degree of substitution 10%) is completely dissolved
In above-mentioned solvent, the ethyl chitosan that concentration is 1.0% is made and is film-made stoste, through on extruding filtering, standing and defoaming, glass plate
40 DEG C of spin-coating, constant temperature constant humidity 50% are dry, ethanol solution impregnates 1.5h and takes off film, distillation water washing to neutrality, and permanent
The operations such as 40 DEG C of constant humidity 50% of temperature are dry, obtain transparent ethyl chitosan film, with a thickness of 1.88 μm, breaking strength
173MPa, elongation at break 3.96%, initial modulus 4.65GPa.
Embodiment 5:
The glycine hydrochloride saline solution 50g for preparing 2.5%, is dissolved completely in above-mentioned solvent for 1.5g ethyl chitosan
In, the ethyl chitosan that concentration is 3.0% is made and is film-made stoste, squeezed filtering, standing and defoaming, spin-coating on glass plate,
40 DEG C of constant humidity 50% of constant temperature are dry, ethanol solution impregnates 2.0h and takes off film, distillation water washing to neutrality, and 40 DEG C of constant humidity of constant temperature
50% operation such as dry, obtains transparent ethyl chitosan film, with a thickness of 1.76 μm, breaking strength 182MPa, extension at break
Rate 3.85%, initial modulus 4.76GPa.
Claims (1)
1. a kind of preparation method of ethyl chitosan film, preparation method are as follows: self-control ethyl chitosan is dissolved in 1 ~ 5% sweet ammonia
In acid hydrochloride aqueous solution, be completely dissolved the ethyl chitosan stoste that 1 ~ 5wt% of concentration is made, through squeeze filtering, discontinuous degassing,
Spin-coating, 40 DEG C of dryings of constant humidity 50% of constant temperature, 1 ~ 5h of soaked in absolute ethyl alcohol take off film, distillation water washing to neutrality on glass plate, and
The dry operation of 40 DEG C of constant humidity 50% of constant temperature, obtains ethyl chitosan film, gained film with a thickness of 1.5 ~ 2 μm, breaking strength >=
150MPa, elongation at break > 3.7%, initial modulus > 4.5GPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610765755.XA CN106380611B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of ethyl chitosan film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610765755.XA CN106380611B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of ethyl chitosan film |
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| Publication Number | Publication Date |
|---|---|
| CN106380611A CN106380611A (en) | 2017-02-08 |
| CN106380611B true CN106380611B (en) | 2019-08-06 |
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| CN201610765755.XA Expired - Fee Related CN106380611B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of ethyl chitosan film |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560741A (en) * | 2012-01-12 | 2012-07-11 | 大连工业大学 | Chitosan and polyvinyl pyrrolidone (PVP) blended fiber and preparation method thereof |
| CN104927070A (en) * | 2015-03-12 | 2015-09-23 | 青岛科技大学 | Preparation method of chitosan membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812743B (en) * | 2010-05-10 | 2012-10-17 | 山东华兴海慈新材料有限公司 | Spinning solution for industrially producing pure chitosan fiber and preparation method thereof |
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2016
- 2016-08-30 CN CN201610765755.XA patent/CN106380611B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560741A (en) * | 2012-01-12 | 2012-07-11 | 大连工业大学 | Chitosan and polyvinyl pyrrolidone (PVP) blended fiber and preparation method thereof |
| CN104927070A (en) * | 2015-03-12 | 2015-09-23 | 青岛科技大学 | Preparation method of chitosan membrane |
Non-Patent Citations (1)
| Title |
|---|
| 纤维素／壳聚糖复合材料的制备与应用研究进展;付冉冉等;《材料导报Ａ：综述篇》;20160810;第30卷(第8期);124-129 |
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| CN106380611A (en) | 2017-02-08 |
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Granted publication date: 20190806 Termination date: 20210830 |