CN102492163A - Preparation method of high-hydrophobicity cellulose membrane - Google Patents
Preparation method of high-hydrophobicity cellulose membrane Download PDFInfo
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- CN102492163A CN102492163A CN2011104436622A CN201110443662A CN102492163A CN 102492163 A CN102492163 A CN 102492163A CN 2011104436622 A CN2011104436622 A CN 2011104436622A CN 201110443662 A CN201110443662 A CN 201110443662A CN 102492163 A CN102492163 A CN 102492163A
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- cellulose
- stearic acid
- pressed stearic
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Abstract
The invention discloses a preparation method of a high-hydrophobicity cellulose membrane. According to the invention, cellulose is dissolved in a low-temperature pre-cooled aqueous solution of NaOH-urea, such that a cellulose solution is prepared; regenerated cellulose gel is prepared by using the cellulose solution; the cellulose gel is positioned in ethanol solutions of stearic acid with different concentrations; the cellulose gel is soaked for 15min; obtained composite gel is subject to hot-press drying under a temperature of 70-110 DEG C and a pressure of 0.1-10MPa, such that the high-hydrophobicity cellulose membrane material is obtained. The cellulose membrane has excellent water resistance and water tolerance, writability, and biodegradability. The cellulose membrane has a wide application prospect in fields of packaging and printing materials.
Description
Technical field
The present invention relates to the preparation method of the plain film of a kind of high hydrophobic fiber, belong to the natural macromolecular material field.
Background technology
Mierocrystalline cellulose is the abundantest renewable resources, yet it is difficult to dissolving.The contriver belongs to the traditional method that the polymer heating for dissolving is broken through in the laboratory, has opened up a kind of brand-new dissolution in low temperature method and mechanism.Utilize NaOH/ aqueous solution of urea low temperature successfully to dissolve the intractable macromole---Mierocrystalline cellulose [Macromolecules, 2008,41,9345].The cellulose solution that we have utilized aqueous systems and dissolution in low temperature to obtain, and develop a series of Mierocrystalline cellulose novel materials comprises the plain film of functional fiber, and prove their fully biodegradables [
Green Chemistry,
2009,11,177].The biological degradability cellulose membrane has broad prospect of application but makes that owing to a large amount of wetting ability hydroxyls on the Mierocrystalline cellulose exist its water resisting property is poor, influences further development and utilization.Therefore it is quite important to improve hydrophobic cellulose property, but the expansion fiber cellulosic material is antifog at water-proof material (for example waterproff keyboard film), the application of aspects such as moisture-proof packaging material.
Summary of the invention
The present invention wants the technical solution problem to provide a kind of simple method to prepare the plain film of high hydrophobic fiber.
The present invention is adopted technical scheme to be by the technical solution problem:
Obtain cellulose gel by cellulose solution regeneration, be soaked in by cellulose gel and process Mierocrystalline cellulose Triple Pressed Stearic Acid plural gel in the Triple Pressed Stearic Acid solution, hot-pressing processing obtains then.
In the hot pressing, consider the Triple Pressed Stearic Acid melt temperature about 70 ℃, molten state is disperseed more even; On the other hand, exert pressure and help cellulose stearate and more combine closely.Consider dispersiveness and bonding state, hot pressing can carry out under the 0.1-10MPa at 70-110 ℃, and it is better under this condition, to make the composite package homogeneity.Hot pressing temperature and hot pressing time are inversely proportional to, and temperature is high more, need the time short more.
Above-mentioned cellulose solution preparation method can adopt the known technology method, not special restriction.For example, for example, said cellulose solution is obtained by LiCl/ N,N-DIMETHYLACETAMIDE, N-methylmorpholine-N-oxide compound (NMMO), ionic liquid, the 9wt%NaOH aqueous solution, LiOH/ urea, NaOH/ thiocarbamide, NaOH/ aqueous solution of urea dissolving cellulos.
As a kind of preferred, cellulose solution is by obtaining in the NaOH/ aqueous solution of urea of cellulose dissolution after precooling.
The gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.
The present invention uses Triple Pressed Stearic Acid solution and is dissolved in common organic solvents by Triple Pressed Stearic Acid, and as a kind of preferred, Triple Pressed Stearic Acid solution is obtained by dissolve with ethanol.
Cellulose gel is placed different concns Triple Pressed Stearic Acid solution, soaked 15 minutes, promptly obtain Mierocrystalline cellulose Triple Pressed Stearic Acid plural gel.
The inventive method adopts cellulose paste dissolving regeneration is obtained cellulose gel, and gel combines to obtain the Mierocrystalline cellulose plural gel with Triple Pressed Stearic Acid in Triple Pressed Stearic Acid solution.Triple Pressed Stearic Acid is in molten state in the plural gel under hot pressing temperature; Be convenient to better dispersion; Lower the temperature the back Triple Pressed Stearic Acid in the cellulose surface crystallization, thereby improve its surfaceness to form uneven surface, these Triple Pressed Stearic Acid crystal of while can be arranged in rod or the sheet structure is made into the multiclass hole; These holes can be caught air (because air and water droplet contact angle are 180 °), and it is quite important for improving the cellulose surface hydrophobicity.Can obtain different shape Triple Pressed Stearic Acid crystal through changing hot pressing temperature and Triple Pressed Stearic Acid concentration; In addition; Triple Pressed Stearic Acid is a kind of wax shape low surface energy material; So do not need further to modify just can obtain super hydrophobic surface, cellulosic contact angle is 48 °, gained composite package contact angle is all more than 125 °.
The obtained cellulose materials of the inventive method has high hydrophobicity, writing property, and waterproof is water-fast and biodegradability.We make the cellulose composite membrane water-repellancy and have excellent water-resistance, and do not need further modification, and technological process is simple, is easy to industriallization.
The practical implementation method
Below will specify the present invention, but these specific embodiments do not limit the present invention in any way protection domain through specific embodiment.Raw material that this embodiment is used is a known compound, can buy in market.(OCA20 Germany) records the Mierocrystalline cellulose contact angle, and saturated water absorption (after 960 minutes) is calculated by weighting method by the contact angle tester.
Embodiment 1
It is freezing to-12.8 that 6-8wt%NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4wt % cellulose solution, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the ethanolic soln, takes out after 15 minutes, and at 0.1MPa, 90
oHot pressing under the C.Gained cellulose materials contact angle is 48 °, and saturated water absorption is 108 wt %.
Embodiment 2
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 5 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 90
oHot pressing under the C.Gained cellulose materials contact angle is 136 °, and saturated water absorption is 50 wt %.
Embodiment 3
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 20 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 90
oHot pressing under the C.Gained cellulose materials contact angle is 142 °, and saturated water absorption is 23 wt %.
Embodiment 4
It is freezing to-12.8 that 6-8% wt NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 40 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 90
oHot pressing under the C.Gained cellulose materials contact angle is 146 °, and saturated water absorption is 18 wt %.
Embodiment 5
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 5 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 70
oHot pressing under the C.Gained cellulose materials contact angle is 131 °, and saturated water absorption is 73wt %.
Embodiment 6
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 5 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 80
oHot pressing under the C.Gained cellulose materials contact angle is 134 °, and saturated water absorption is 60 wt %.
Embodiment 7
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 5 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 100
oHot pressing under the C.Gained cellulose materials contact angle is 136 °, and saturated water absorption is 52 wt %.
Embodiment 8
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 5 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 0.1MPa, 110
oHot pressing under the C.Gained cellulose materials contact angle is 134 °, and saturated water absorption is 62 wt %.
Embodiment 9
It is freezing to-12.8 that 6-8 wt %NaOH, 10-14 wt % urea and water are formed solvent system
oC, dissolving cellulos obtain 4 wt % cellulose solutions, and the gained cellulose solution obtains cellulose gel through 5 wt% sulfuric acid/10 wt% aqueous sodium persulfate solutions regeneration after cleaning.This cellulose aquagel is immersed in the 5 wt % Triple Pressed Stearic Acid ethanolic solns, takes out after 15 minutes, the gained plural gel is at 10MPa, 90
oHot pressing under the C.Gained cellulose materials contact angle is 128 °, and saturated water absorption is 77 wt %.
Claims (7)
1. a method for preparing the plain film of high hydrophobic fiber is characterized in that, obtains cellulose gel by cellulose solution regeneration, is soaked in by cellulose gel and processes Mierocrystalline cellulose Triple Pressed Stearic Acid plural gel in the Triple Pressed Stearic Acid solution, and hot-pressing processing obtains then.
2. method according to claim 1 is characterized in that, hot pressing carries out under the 0.1-10MPa at 70-110 ℃.
3. method according to claim 1 and 2; It is characterized in that said cellulose solution is obtained by LiCl/ N,N-DIMETHYLACETAMIDE, N-methylmorpholine-N-oxide compound, ionic liquid, the 9wt%NaOH aqueous solution, LiOH/ urea, NaOH/ thiocarbamide, NaOH/ aqueous solution of urea dissolving cellulos.
4. method according to claim 3 is characterized in that, cellulose solution is by obtaining in the NaOH/ aqueous solution of urea of cellulose dissolution after precooling.
5. method according to claim 1 and 2 is characterized in that, cellulose gel is placed Triple Pressed Stearic Acid solution, soaks 15 minutes, promptly obtains Mierocrystalline cellulose Triple Pressed Stearic Acid plural gel.
6. method according to claim 1 and 2 is characterized in that, said Triple Pressed Stearic Acid solution is dissolved in organic solvent by Triple Pressed Stearic Acid and obtains.
7. method according to claim 6 is characterized in that, said Triple Pressed Stearic Acid solution is dissolved in ethanol by Triple Pressed Stearic Acid and obtains.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055347A (en) * | 2013-01-21 | 2013-04-24 | 武汉大学 | Preparation method of cellulose gel material of onion structure |
| CN103257140A (en) * | 2013-05-23 | 2013-08-21 | 潍坊恒联玻璃纸有限公司 | Method for detecting ionic liquid residual amount in regenerated cellulose membrane |
| CN104194059A (en) * | 2014-08-08 | 2014-12-10 | 华中科技大学 | Cellulose thermoplastic material and preparation method thereof |
| CN104356356A (en) * | 2014-11-28 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose hydrophobic material |
| US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
| US8986501B2 (en) | 2012-08-20 | 2015-03-24 | Celanese International Corporation | Methods for removing hemicellulose |
| CN107840977A (en) * | 2017-10-20 | 2018-03-27 | 天津市宝德包装有限公司 | A kind of fresh-keeping preparation method with oxygen flow moisture-inhibiting packaging film of vegetables and fruits |
| CN112552539A (en) * | 2020-12-10 | 2021-03-26 | 四川三联新材料有限公司 | Low-adsorption hydrophobic cellulose membrane and preparation method and application thereof |
| CN113024866A (en) * | 2021-03-19 | 2021-06-25 | 浙江理工大学 | Daytime passive radiation refrigeration hydrophobic cellulose material with anisotropic structure and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
| US8986501B2 (en) | 2012-08-20 | 2015-03-24 | Celanese International Corporation | Methods for removing hemicellulose |
| CN103055347A (en) * | 2013-01-21 | 2013-04-24 | 武汉大学 | Preparation method of cellulose gel material of onion structure |
| CN103055347B (en) * | 2013-01-21 | 2014-09-03 | 武汉大学 | Preparation method of cellulose gel material of onion structure |
| CN103257140A (en) * | 2013-05-23 | 2013-08-21 | 潍坊恒联玻璃纸有限公司 | Method for detecting ionic liquid residual amount in regenerated cellulose membrane |
| CN104194059A (en) * | 2014-08-08 | 2014-12-10 | 华中科技大学 | Cellulose thermoplastic material and preparation method thereof |
| CN104194059B (en) * | 2014-08-08 | 2017-07-11 | 华中科技大学 | A kind of cellulose thermoplastic material and preparation method thereof |
| CN104356356A (en) * | 2014-11-28 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose hydrophobic material |
| CN107840977A (en) * | 2017-10-20 | 2018-03-27 | 天津市宝德包装有限公司 | A kind of fresh-keeping preparation method with oxygen flow moisture-inhibiting packaging film of vegetables and fruits |
| CN112552539A (en) * | 2020-12-10 | 2021-03-26 | 四川三联新材料有限公司 | Low-adsorption hydrophobic cellulose membrane and preparation method and application thereof |
| CN113024866A (en) * | 2021-03-19 | 2021-06-25 | 浙江理工大学 | Daytime passive radiation refrigeration hydrophobic cellulose material with anisotropic structure and preparation method thereof |
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Application publication date: 20120613 |