CN105801921A - Cellulose esterification derivative ordered porous membrane material and preparation method thereof - Google Patents
Cellulose esterification derivative ordered porous membrane material and preparation method thereof Download PDFInfo
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- CN105801921A CN105801921A CN201410845721.2A CN201410845721A CN105801921A CN 105801921 A CN105801921 A CN 105801921A CN 201410845721 A CN201410845721 A CN 201410845721A CN 105801921 A CN105801921 A CN 105801921A
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Abstract
The invention relates to a cellulose esterification derivative ordered porous membrane material and a preparation method thereof. The material is an esterification modifier of cellulose acetate, can simply and efficiently form an ordered porous structure at high humidity, can easily form an ordered porous membrane, and can be used as a porous membrane material needed by 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
The thin polymer film with micro nano structure all has critically important using value in biomaterial, photoelectric material etc., thus being widely studied and application.Past, preparation has the thin film of micro nano structure can adopt different template methods, the templates such as such as Colloidal crystals, emulsion droplet, biological bacterium and filter membrane, but due to reasons such as its preparation process is complicated, template size is fixed, template preparation difficulties, therefore hardly result in the thin film with adjustable dimension or single dispersing structure.nullIn recent years，WidawskiG..RawisoM.andFrancoisB. new method [the Self-OrganizedHoneycombMorphologyofStar-PolymerPolystyre neFilms.Nature369 preparing the thin film with microstructure under high humidity conditions reported,387 ~ 389 (1994)] developed gradually，And because it is simply controlled，Increasingly it is subject to concern [the Breathfiguresasadynamictemplatingmethodforpolymersandnan omaterials.AdvancedMaterials18 of people,973~989(2006)】.By this method, different polymer can be utilized to prepare the perforated membrane [Formationofhoneycomb-structured of high-sequential, porousfilmsviabreathfigureswithdifferentpolymerarchitect ures.JournalofPolymerSciencePartA:PolymerChemistry44,2363 ~ 2375 (2006)].
Cellulose is the natural polymer that nature enriches the most, its most important application is exactly as thin-film material, many fields such as thin film and porous material [Morphologyandpermeabilityofcellulose/chitinblendmembrane s.JournalofMembraneScience287,19 ~ 28 (2007)] it have been widely applied to such as regenerated cellulose.But, utilize simple cellulosic structure to hardly result in the cellulose base thin film of orderly pore structure, significantly hinder the cellulosic material application at film applications.By changing cellulosic structure, it is expected to provide a kind of new way for the preparation of cellulose ordered porous membrane.But, it is used for preparing that ordered porous membrane cellulosic material kind is few and structure is more complicated, greatly limit the application in different field of this type of cellulosic material.
Summary of the invention
One purpose of the present invention is in that to provide a kind of cellulose derivative material for preparing ordered porous membrane.
Another object of the present invention is to the preparation method that a kind of cellulose derivative material preparing ordered porous membrane is provided.
It is still another object of the present invention to provide a kind of cellulose derivative material and prepare the short-cut method of ordered porous membrane.
The present invention is a kind of cellulose esterification derivative for preparing the cellulose derivative material of ordered porous membrane, and its structural formula is:
Wherein:
R1For CH3CO；
R2For R3CO、CH3CO or H, wherein R3For the carbon number alkyl chain be more than or equal to 4；
R2Middle R3CO、CH3The ratio of CO or H three, wherein R3CO ratio 20 ~ 100%, CH3CO ratio is 0 ~ 60%, and H ratio is 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, oxolane will fully dissolve cellulose acetate, add pyridine, triethylamine acid binding agent, react with the tetrahydrofuran solution of alkane carboxylic acid halides under ice-water bath, synthetic vinegar acid cellulose derivant, wherein on cellulose acetate, the mol ratio of residual hydroxyl and alkane carboxylic acid halides is 1:1 ~ 1:10；After reacting 4 ~ 24 hours under ice-water bath, in room temperature continuation reaction 48 ~ 72 hours, being subsequently adding water and terminate reaction, reaction mixture precipitates, filters, dries, and obtains cellulose esterification modification derivant.
The preparation method of the cellulose derivative ordered porous membrane of the present invention comprises the following steps:
Weigh a certain amount of cellulose derivative to be completely dissolved in volatile organic solvent, be made into the solution of 0.1～100 g/l；Relative humidity be 30 ~ 95%, temperature be 0 ~ 50 degree Celsius environment under, solution of cellulose derivative is dripped in planar substrates, natural drying film forming, obtains the perforated membrane with ordered porous structural.
The orderly pore membrane prepared based on cellulose derivative material of the present invention, this membrane material has abundance, environmental friendliness, pollution-free, membrane material preparation method is simple, and method for preparing porous film is convenient and simple, and the feature such as the perforated membrane degree of order is good, the needs of different field application can be met.
Accompanying drawing explanation
Fig. 1. when the embodiment of the present invention 1 is used for preparing perforated membrane, its pore structure has high-sequential.
Fig. 2. when the embodiment of the present invention 2 is used for preparing perforated membrane, its pore structure has high-sequential.
Detailed description of the invention
Embodiment1:
(1) preparation of cellulose derivative
A. weighing 1 gram of cellulose acetate, its number-average molecular weight is 30000, and acetyl content is 39.8%, joins in 10 milliliters of oxolanes, is stirred well to and is completely dissolved under room temperature.
B., after fully dissolving, in mixed liquor, add the pyridine of 0.5 milliliter, be sufficiently stirred for mix homogeneously.
C. configure the tetrahydrofuran solution 2 milliliters containing 250 milligrams of bromine isobutyl acylbromides, be slowly added dropwise in continuously stirred cellulose acetate/tetrahydrofuran solution under ice-water bath, drip to finish under ice-water bath, continue stirring 6 hours, more at room temperature continue stirring 48 hours.
D. reaction mixture joins 50 milliliters of water termination reactions, is precipitated product.
E. precipitated product dissolves again with oxolane, aqueous precipitation, repeatedly dissolution precipitation three times, is finally placed in 50 degrees Celsius of vacuum drying ovens dry, obtains cellulose esterification modification derivant.
(2) preparation of cellulose esterification derivative ordered porous membrane
A. weigh 100 milligrams of cellulose esterification derivatives, join in 10 milliliters of dichloromethane, fully dissolve, be made into the dichloromethane solution of 10 g/l.
B. relative humidity be 70%, temperature be 22 degrees Celsius environment under, measure the solution obtained in 50 microlitre step a, drip on the sheet glass cleaned up, natural drying film forming, obtain the poroid thin film with ordered porous structural.
Embodiment2:
(1) preparation process of cellulose derivative is with embodiment 1
A. weighing 1 gram of cellulose acetate, its number-average molecular weight is 50000, and acetyl content is 39.7%, joins in 15 milliliters of oxolanes, is stirred well to and is completely dissolved under room temperature.
B., after fully dissolving, in mixed liquor, add the pyridine of 1.0 milliliters, be sufficiently stirred for mix homogeneously.
C. configure the tetrahydrofuran solution 4 milliliters containing 500 milligrams of valeric chlorides, be slowly added dropwise in continuously stirred cellulose acetate/tetrahydrofuran solution under ice-water bath, drip to finish under ice-water bath, continue stirring 12 hours, more at room temperature continue stirring 72 hours.
D. reaction mixture joins 100 milliliters of water termination reactions, is precipitated product.
E. precipitated product dissolves again with oxolane, aqueous precipitation, repeatedly dissolution precipitation three times, is finally placed in 50 degrees Celsius of vacuum drying ovens dry, obtains cellulose esterification modification derivant.
(2) preparation process of cellulose esterification derivative ordered porous membrane is with embodiment 1
A. weigh 50 milligrams of cellulose esterification derivatives, join in 10 milliliters of dichloromethane, fully dissolve, be made into the dichloromethane solution of 5 g/l.
B. relative humidity be 75%, temperature be 20 degrees Celsius environment under, measure the solution obtained in 20 microlitre step a, drip on the sheet glass cleaned up, natural drying film forming, obtain the poroid thin film with ordered porous structural.
The cellulose esterification modification derivant that will obtain, wiring solution-forming in easy volatile solvent, solution is dripped in sheet glass film forming under certain relative humidities, during by its membrane superficial tissue of observation by light microscope (as shown in Figure 1, Figure 2), demonstrate it to have and be easily formed ordered porous membrane architectural characteristic well, its process preparing ordered porous membrane is simple and convenient, can be used for the highly ordered porous materials that template and cell culture growth etc. need.
Claims (3)
1. a cellulose esterification derivative ordered porous membrane material, is characterized in that, described material is cellulose acetate esterification derivant, and its structural formula is:
Wherein:
R1For CH3CO；
R2For R3CO、CH3CO or H, wherein R3For the carbon number alkyl chain more than or equal to 4；
R2Middle R3CO、CH3The ratio of CO or H three, wherein R3CO ratio 20 ~ 100%, CH3CO ratio is 0 ~ 70%, and H ratio is 0 ~ 10%.
2. the preparation method of ordered porous membrane cellulose according to claim 1 esterification derivant material, is characterized in that, this preparation method comprises the following steps:
Under 25 ~ 50 degrees Celsius, oxolane will fully dissolve cellulose acetate, add pyridine, triethylamine acid binding agent, react with the tetrahydrofuran solution of alkane carboxylic acid halides under ice-water bath, synthetic vinegar acid cellulose derivant, wherein on cellulose acetate, the mol ratio of residual hydroxyl and alkane carboxylic acid halides is 1:1 ~ 1:10；After reacting 4 ~ 24 hours under ice-water bath, in room temperature continuation reaction 48 ~ 72 hours, being subsequently adding water and terminate reaction, reaction mixture precipitates, filters, dries, and obtains cellulose esterification modification derivant.
3. the preparation method of cellulose esterification derivative ordered porous membrane according to claim 1, is characterized in that, this preparation method comprises the following steps:
Weigh a certain amount of cellulose derivative to be completely dissolved in volatile organic solvent, be made into the solution of 0.1～100 g/l；Relative humidity be 30 ~ 95%, temperature be 0 ~ 50 degree Celsius environment under, solution of cellulose derivative is dripped in planar substrates, natural drying film forming, obtains the perforated membrane with ordered porous structural.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
| 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 |
| 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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