CN105801921B - A kind of cellulose esterification derivative ordered porous membrane material and preparation method thereof - Google Patents
A kind of cellulose esterification derivative ordered porous membrane material and preparation method thereof Download PDFInfo
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- CN105801921B CN105801921B CN201410845721.2A CN201410845721A CN105801921B CN 105801921 B CN105801921 B CN 105801921B CN 201410845721 A CN201410845721 A CN 201410845721A CN 105801921 B CN105801921 B CN 105801921B
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Abstract
The present invention relates to a kind of cellulose esterification derivative ordered porous membrane material and preparation method thereof.Described material is the esterification modification thing of cellulose acetate, the material under high humidity conditions can simple and effective form ordered porous structural, there is the characteristic for easily forming ordered porous membrane, can be used as the porous film material of the needs such as template and cell growth.
Description
Technical field
The present invention relates to a kind of cellulose esterification 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, so as to be widely studied and apply.In the past, different template sides can be used by preparing the film with micro nano structure
Method, such as the template such as Colloidal crystals, emulsion droplet, biological bacterium and filter membrane, but because 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 single dispersing structure.In recent years,
Widawski G.. Rawiso M. and Francois B. reports are prepared with microstructure under high humidity conditions
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, 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 its 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 changing the structure of cellulose, be expected to for cellulose it is more in order
The preparation of pore membrane provides a kind of new way.However, for prepare that ordered porous membrane cellulosic material species is few and structure compared with
Complexity, it greatly limit application of such cellulosic material in different field.
The content of the invention
The purpose of the present invention is to provide a kind of cellulose derivative material for being used to prepare ordered porous membrane.
Another object of the present invention is to provide a kind of preparation side for the cellulose derivative material for preparing ordered porous membrane
Method.
It is still another object of the present invention to provide the short-cut method that a kind of cellulose derivative material prepares ordered porous membrane.
The cellulose derivative material for being used to prepare ordered porous membrane of the present invention is a kind of cellulose esterification derivative, its
Structural formula is：
Wherein：
R1For CH3CO；
R2For R3CO、CH3CO or H, wherein R3It is more than or equal to 4 alkyl chain for carbon number；
R2Middle R3CO、CH3The ratio of CO or H threes, wherein R3CO ratios 20 ~ 100%, CH3CO ratios are 0 ~ 60%, H ratios
For 0 ~ 10%.
N represents the degree of polymerization.
The preparation method of the cellulose derivative material for preparing ordered porous membrane of the present invention comprises the following steps：
Under 25 ~ 50 degrees Celsius, cellulose acetate will be fully dissolved in tetrahydrofuran, adds pyridine, triethylamine ties up acid
Agent, the tetrahydrofuran solution with alkane carboxylic acid halides under ice-water bath react, and cellulose acetate derivative are synthesized, wherein on cellulose acetate
Residual hydroxyl and the mol ratio of alkane carboxylic acid halides are 1:1~1:10；After being reacted 4 ~ 24 hours under ice-water bath, continue reaction 48 ~ 72 in room temperature
Hour, water terminating reaction is then added, reaction mixture precipitation, filtering, is dried, obtains cellulose esterification modification derivant.
The preparation method of the cellulose derivative ordered porous membrane of the present invention comprises the following steps：
A certain amount of cellulose derivative is weighed to be completely dissolved in volatile organic solvent, be made into 0.1~100 gram/
The solution risen；Be in the environment of 30 ~ 95%, temperature is 0 ~ 50 degree Celsius in relative humidity, by solution of cellulose derivative be added dropwise in
In planar substrates, film forming is spontaneously dried, obtains the perforated membrane with ordered porous structural.
The orderly pore membrane prepared based on cellulose derivative material of the present invention, the membrane material have abundance, environment
It is friendly, pollution-free, the features such as membrane material preparation method for material is simple, and method for preparing porous film is convenient and simple, and the perforated membrane degree of order is good,
The needs of different field application can be met.
Brief description of the drawings
When Fig. 1 embodiment of the present invention 1 is used to prepare perforated membrane, its pore structure has high-sequential.
When Fig. 2 embodiment of the present invention 2 is used to prepare perforated membrane, its pore structure has high-sequential.
Embodiment
Embodiment 1：
（1）The preparation of cellulose derivative
A. 1 gram of cellulose acetate is weighed, its number-average molecular weight is 30000, acetyl content 39.8%, is added to 10 millis
Rise in tetrahydrofuran, be stirred well to be completely dissolved at room temperature.
B. fully after dissolving, 0.5 milliliter of pyridine is added into mixed liquor, is thoroughly mixed uniformly.
C. tetrahydrofuran solution 2 milliliter of the configuration containing 250 milligrams of bromine isobutyl acylbromides, is slowly dropped under ice-water bath and holds
In cellulose acetate/tetrahydrofuran solution of continuous stirring, drop finishes continues stirring 6 hours under ice-water bath, then continues at room temperature
Stirring 48 hours.
D. reaction mixture is added to 50 milliliters of water terminating reactions, obtains precipitated product.
E. precipitated product reuses tetrahydrofuran dissolving, aqueous precipitation, and dissolving repeatedly precipitates three times, is finally placed in 50
Dried in degree Celsius vacuum drying chamber, obtain cellulose esterification modification derivant.
（2）The preparation of cellulose esterification derivative ordered porous membrane
A. 100 milligrams of cellulose esterification derivatives are weighed, are added in 10 milliliters of dichloromethane, fully dissolving, are made into 10
G/l dichloromethane solution.
B. in the environment of relative humidity is 70%, temperature is 22 degrees Celsius, the solution obtained in 50 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 cellulose derivative is the same as embodiment 1
A. 1 gram of cellulose acetate is weighed, its number-average molecular weight is 50000, acetyl content 39.7%, is added to 15 millis
Rise in tetrahydrofuran, be stirred well to be completely dissolved at room temperature.
B. fully after dissolving, 1.0 milliliters of pyridine is added into mixed liquor, is thoroughly mixed uniformly.
C. tetrahydrofuran solution 4 milliliter of the configuration containing 500 milligrams of valeric chlorides, is slowly dropped under ice-water bath and persistently stirs
In the cellulose acetate/tetrahydrofuran solution mixed, drop finishes continues stirring 12 hours under ice-water bath, then continues to stir at room temperature
72 hours.
D. reaction mixture is added to 100 milliliters of water terminating reactions, obtains precipitated product.
E. precipitated product reuses tetrahydrofuran dissolving, aqueous precipitation, and dissolving repeatedly precipitates three times, is finally placed in 50
Dried in degree Celsius vacuum drying chamber, obtain cellulose esterification modification derivant.
（2）The preparation process of cellulose esterification derivative ordered porous membrane is the same as embodiment 1
A. 50 milligrams of cellulose esterification derivatives are weighed, are added in 10 milliliters of dichloromethane, fully dissolving, be made into 5 grams/
The dichloromethane solution risen.
B. in the environment of relative humidity is 75%, temperature is 20 degrees Celsius, the solution obtained in 20 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.
Obtained cellulose is esterified modification derivant, the wiring solution-forming in easy volatile solvent, in certain relative humidity
Under the conditions of solution is dripped in sheet glass film forming, during by its membrane superficial tissue of observation by light microscope（As shown in Figure 1, Figure 2）, it was demonstrated that
It has easily forms orderly porous membrane structure characteristic well, and it is simple and convenient that it prepares the process of ordered porous membrane, available for mould
The highly ordered porous materials of the needs such as plate and cell culture growth.
Claims (3)
1. a kind of cellulose esterification derivative ordered porous membrane material, it is characterized in that, the material is that cellulose acetate esterification is spread out
Biology, its structural formula are：
Wherein：
R1For CH3CO；
R2For R3CO、CH3CO or H, wherein R3It is more than or equal to 4 alkyl chain for carbon number；
R2Middle R3CO、CH3The ratio of CO or H threes, wherein R3CO ratios 20 ~ 100%, CH3CO ratios be 0 ~ 70%, H ratios be 0 ~
10%。
2. cellulose esterification derivative ordered porous membrane material according to claim 1, it is characterized in that, the preparation of the material
Method comprises the following steps：
Under 25 ~ 50 degrees Celsius, cellulose acetate is fully dissolved in tetrahydrofuran, pyridine, triethylamine acid binding agent are added, in ice
Tetrahydrofuran solution under water-bath with alkane carboxylic acid halides reacts, and synthesizes cellulose acetate derivative, hydroxyl is wherein remained on cellulose acetate
The mol ratio of base and alkane carboxylic acid halides is 1:1~1:10；After being reacted 4 ~ 24 hours under ice-water bath, continue reaction 48 ~ 72 hours in room temperature,
Then water terminating reaction is added, reaction mixture precipitation, filtering, is dried, obtains cellulose esterification modification derivant.
3. cellulose esterification derivative ordered porous membrane material according to claim 1, it is characterized in that, utilize the material system
The method of standby ordered porous membrane comprises the following steps：
Weigh a certain amount of cellulose derivative to be completely dissolved in volatile organic solvent, be made into 0.1~100 g/l
Solution；It is that in the environment of 30 ~ 95%, temperature is 0 ~ 50 degree Celsius, solution of cellulose derivative is added dropwise in plane in relative humidity
In substrate, film forming is spontaneously dried, obtains the perforated membrane with ordered porous structural.
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| CN108034069A (en) * | 2017-12-27 | 2018-05-15 | 湖南工业大学 | A kind of phenylacetyl cellulose acetate ordered porous membrane material and preparation method thereof |
| CN108329510A (en) * | 2018-01-10 | 2018-07-27 | 湖南工业大学 | A kind of acetylation cellulose acetate ordered porous membrane material and preparation method thereof |
| CN112194733A (en) * | 2019-07-08 | 2021-01-08 | 湖南工业大学 | Cellulose-based silane derivative ordered porous membrane material and preparation method thereof |
| 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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Inventor after: Shi Junhua Inventor after: Liu Wenyong Inventor after: Zhou Zhihan Inventor after: Yang Mingming Inventor after: Chen Yi Inventor after: Liu Yuejun Inventor before: Liu Wenyong Inventor before: Chen Yi Inventor before: Liu Yuejun |
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Effective date of registration: 20201221 Address after: No.18 Xiangyang Road, Gangkou street, Gaogang District, Taizhou City, Jiangsu Province Patentee after: Wang Yajun Address before: 412007 No. 88 Taishan Road, Tianyuan District, Zhuzhou City, Hunan Province Patentee before: HUNAN University OF TECHNOLOGY |
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Effective date of registration: 20211125 Address after: 710000 Room 408, 4th floor, building B1, standard workshop community, textile industrial park, Baqiao District, Xi'an City, Shaanxi Province Patentee after: Shaanxi future biological matrix Engineering Co.,Ltd. Address before: No.18 Xiangyang Road, Gangkou street, Gaogang District, Taizhou City, Jiangsu Province Patentee before: Wang Yajun |
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