CN108329510A - A kind of acetylation cellulose acetate ordered porous membrane material and preparation method thereof - Google Patents
A kind of acetylation cellulose acetate ordered porous membrane material and preparation method thereof Download PDFInfo
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- CN108329510A CN108329510A CN201810020932.0A CN201810020932A CN108329510A CN 108329510 A CN108329510 A CN 108329510A CN 201810020932 A CN201810020932 A CN 201810020932A CN 108329510 A CN108329510 A CN 108329510A
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- cellulose acetate
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
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Abstract
The present invention relates to a kind of acetylation cellulose acetate ordered porous membrane materials and preparation method thereof.The material is acetylation cellulose acetate, the material under high humidity conditions can high-efficient simple form ordered porous structural, there is the characteristic for easily forming ordered porous membrane.Moreover, the features such as acetylation cellulose acetate ordered porous membrane material of the present invention has abundance, environmental-friendly, pollution-free, and membrane material preparation method for material is simple, method for preparing porous film is easy, the perforated membrane degree of order is high, can meet the needs of different field application.
Description
Technical field
Invention is related to a kind of cellulose derivative ordered porous membrane material and preparation method thereof.
Background technology
Thin polymer film with micro nano structure is in biomaterial, photoelectric material etc. all with critically important application
Value, to be widely studied and apply.Past prepares the film with micro nano structure and different template sides may be used
The templates such as method, such as Colloidal crystals, emulsion droplet, biological bacterium and filter membrane, but since its preparation process is complicated, template size
Fixed, template prepares the reasons such as difficulty, therefore hardly results in the film with adjustable dimension or monodisperse structure.In recent years,
Preparing under high humidity conditions for Widawski G.. Rawiso M. and Francois B. reports is thin with microstructure
The new method of film【Self-Organized Honeycomb Morphology of Star-Polymer Polystyrene
Films. Nature 369, 387~389(1994)】Gradually developed, and because it is simple controllable, increasingly by people
Concern【Breath figures as a dynamic templating method for polymers and
nanomaterials. Advanced Materials 18, 973~989(2006)】.By this method, it can utilize not
The perforated membrane of high-sequential is prepared with polymer【Formation of honeycomb-structured, porous
films via breath figures with different polymer architectures. Journal of
Polymer Science Part A: Polymer Chemistry 44, 2363~2375(2006)】。
Cellulose is nature natural polymer the abundantest, and a most important application is exactly to be used as film material
Material, such as regenerated cellulose have been widely applied to film and many fields of porous material【Morphology and
permeability of cellulose/chitin blend membranes. Journal of Membrane Science
287, 19~28(2007)】.However, the cellulose base film of orderly pore structure is hardly resulted in using simple cellulosic structure,
Application of the cellulosic material in film applications is hindered significantly.By change cellulose structure, be expected to for cellulose it is orderly more
The preparation of pore membrane provides a kind of new way.However, the cellulosic material type for being used to prepare ordered porous membrane is few and structure compared with
Complexity greatly limits application of such cellulosic material in different field.
Invention content
The one of the present invention is designed to provide a kind of acetylation cellulose acetate ordered porous membrane material.
Another object of the present invention is to provide a kind of preparation methods of acetylation cellulose acetate ordered porous membrane material.
It is still another object of the present invention to provide the simplicity that a kind of acetylation cellulose acetate material prepares ordered porous membrane
Method.
The cellulose derivative material for being used to prepare ordered porous membrane of the present invention is acetylation cellulose acetate, structure
Formula is：
Wherein：
R1For CH3CO；
R2For CH3CO or H；
In R1And R2Three substituent groups in, CH3Degree of substitution of the degree of substitution of CO more than or equal to 2.6, H is less than or equal to 0.4.
The preparation method of the acetylation cellulose acetate material for being used to prepare ordered porous membrane of the present invention includes following step
Suddenly：
Under 25 ~ 50 degrees Celsius, cellulose acetate is dissolved in tetrahydrofuran, pyridine, triethylamine acid binding agent is added, in ice-water bath
Lower to be reacted with the tetrahydrofuran solution of acetyl halide, wherein the molar ratio of the hydroxyl on cellulose acetate and acetyl halide is 1:0.5~1:
10；After being reacted 4 ~ 24 hours under ice-water bath, in room temperature, the reaction was continued 48 ~ 72 hours, and water is then added and terminates reaction, reaction mixing
Liquid precipitate, filtering, drying obtain acetylation cellulose acetate.
The preparation method packet that ordered porous membrane is prepared using acetylation cellulose acetate ordered porous membrane material of the present invention
Include following steps：
It weighs a certain amount of acetylation cellulose acetate to be dissolved in volatile organic solvent, is made into 0.1~100 grams per liter
Solution；In the environment of it is 0 ~ 50 degree Celsius that relative humidity, which is 30 ~ 95%, temperature, by acetylation cellulose acetate solution be added dropwise in
In planar substrates, film forming is spontaneously dried, the perforated membrane with ordered porous structural is obtained.
The acetylation cellulose acetate ordered porous membrane material of the present invention has abundance, environmental-friendly, pollution-free, film
The features such as material preparation method is simple, method for preparing porous film is easy, the perforated membrane degree of order is high can meet different field application
It needs.
Description of the drawings
When Fig. 1 embodiment of the present invention 1 is used to prepare perforated membrane, pore structure has high-sequential.
When Fig. 2 embodiment of the present invention 2 is used to prepare perforated membrane, pore structure has high-sequential.
Specific implementation mode
Embodiment 1：
（1）The preparation of acetylation cellulose acetate
A. 2.2 grams of cellulose acetates are weighed, are added in 25.0 milliliters of tetrahydrofurans, at room temperature stirring and dissolving.
B. after dissolving, 0.8 milliliter of pyridine is added into mixed liquor, is uniformly mixed.
C. tetrahydrofuran solution 4.0 milliliter of the configuration containing 0.7 milliliter of chloroacetic chloride is slowly dropped under ice-water bath and continues
In cellulose acetate/tetrahydrofuran solution of stirring.Drop finishes, and continues stirring 6 hours under ice-water bath, then continue to stir at room temperature
It mixes 48 hours.
D. reaction mixture is added to 150 milliliters of water and terminates reaction, obtains precipitated product.
E. precipitated product utilizes tetrahydrofuran to dissolve again, aqueous precipitation, and dissolving precipitation three times, is finally placed in 50 repeatedly
It is dry in degree Celsius vacuum drying chamber, obtain acetylation cellulose acetate.
（2）The preparation of acetylation cellulose acetate ordered porous membrane
A. 100 milligrams of acetylation cellulose acetates are weighed, are added in 10 milliliters of dichloromethane, fully dissolves, is made into 10 grams per liters
Dichloromethane solution.
B. in the environment of relative humidity is 70%, temperature is 22 degrees Celsius, the solution obtained in 25 microlitres of step a is measured,
It is added dropwise on the sheet glass cleaned up, spontaneously dries film forming, obtain the poroid film with ordered porous structural.
Embodiment 2：
（1）The preparation process of acetylation cellulose acetate is the same as embodiment 1
A. 2.0 grams of cellulose acetates are weighed, are added in 25.0 milliliters of tetrahydrofurans, at room temperature stirring and dissolving.
B. after dissolving, 1.0 milliliters of pyridine is added into mixed liquor, is uniformly mixed.
C. tetrahydrofuran solution 3.0 milliliter of the configuration containing 1.4 milliliters of chloroacetic chlorides is slowly dropped under ice-water bath and continues
In cellulose acetate/tetrahydrofuran solution of stirring.Drop finishes, and continues stirring 12 hours under ice-water bath, then continue at room temperature
Stirring 72 hours.
D. reaction mixture is added to 150 milliliters of water and terminates reaction, obtains precipitated product.
E. precipitated product utilizes tetrahydrofuran to dissolve again, aqueous precipitation, and dissolving precipitation three times, is finally placed in 50 repeatedly
It is dry in degree Celsius vacuum drying chamber, obtain acetylation cellulose acetate.
（2）The preparation process of acetylation cellulose acetate ordered porous membrane is the same as embodiment 1
A. 130 milligrams of phenylacetyl cellulose acetates are weighed, are added in 10 milliliters of dichloromethane, fully dissolve, be made into 13 grams/
The dichloromethane solution risen.
B. in the environment of relative humidity is 88%, temperature is 20 degrees Celsius, the solution obtained in 25 microlitres of step a is measured,
It is added dropwise on the sheet glass cleaned up, spontaneously dries film forming, obtain the poroid film with ordered porous structural.
The acetylation cellulose acetate that will be obtained, the wiring solution-forming in easy volatile solvent, in certain relative humidities
It is lower that solution drop forms a film in sheet glass, when by optical microphotograph sem observation membrane superficial tissue（As shown in Figure 1, Figure 2）, it was demonstrated that it has
Easily form the characteristic of orderly porous membrane structure well, the process for preparing ordered porous membrane is simple and convenient, can be used for template and
The highly ordered porous materials of the needs such as cell culture growth.
Claims (3)
1. a kind of acetylation cellulose acetate ordered porous membrane material, characterized in that the material is acetylation cellulose acetate,
Its structural formula is：
Wherein：
R1For CH3CO；
R2For CH3CO or H；
In R1And R2Three substituent groups in, CH3Degree of substitution of the degree of substitution of CO more than or equal to 2.6, H is less than or equal to 0.4.
2. acetylation cellulose acetate ordered porous membrane material according to claim 1, characterized in that the preparation of the material
Method includes the following steps：
Under 25 ~ 50 degrees Celsius, cellulose acetate is dissolved in tetrahydrofuran, pyridine, triethylamine acid binding agent is added, in ice-water bath
Lower to be reacted with the tetrahydrofuran solution of acetyl halide, wherein the molar ratio of the hydroxyl on cellulose acetate and acetyl halide is 1:0.5~1:
10；After being reacted 4 ~ 24 hours under ice-water bath, in room temperature, the reaction was continued 48 ~ 72 hours, and water is then added and terminates reaction, reaction mixing
Liquid precipitate, filtering, drying obtain acetylation cellulose acetate.
3. acetylation cellulose acetate ordered porous membrane material according to claim 1, characterized in that utilize the material system
The method of standby ordered porous membrane includes the following steps：
It weighs a certain amount of acetylation cellulose acetate to be dissolved in volatile organic solvent, is made into 0.1~100 grams per liter
Solution；In the environment of it is 0 ~ 50 degree Celsius that relative humidity, which is 30 ~ 95%, temperature, by acetylation cellulose acetate solution be added dropwise in
In planar substrates, film forming is spontaneously dried, the perforated membrane with ordered porous structural is obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218016A (en) * | 2019-07-11 | 2020-06-02 | 湖南工业大学 | High-hydrophobicity cellulose-based derivative ordered porous membrane material and preparation method thereof |
| CN112574466A (en) * | 2019-09-27 | 2021-03-30 | 湖南工业大学 | Method for regulating and controlling structural order degree of porous membrane of cellulose acetate derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801921A (en) * | 2014-12-31 | 2016-07-27 | 湖南工业大学 | Cellulose esterification derivative ordered porous membrane material and preparation method thereof |
-
2018
- 2018-01-10 CN CN201810020932.0A patent/CN108329510A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801921A (en) * | 2014-12-31 | 2016-07-27 | 湖南工业大学 | Cellulose esterification derivative ordered porous membrane material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218016A (en) * | 2019-07-11 | 2020-06-02 | 湖南工业大学 | High-hydrophobicity cellulose-based derivative ordered porous membrane material and preparation method thereof |
| CN112574466A (en) * | 2019-09-27 | 2021-03-30 | 湖南工业大学 | Method for regulating and controlling structural order degree of porous membrane of cellulose acetate derivative |
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