CN103319738A - Method for preparing regenerated cellulose composite membrane by crop straws - Google Patents
Method for preparing regenerated cellulose composite membrane by crop straws Download PDFInfo
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- CN103319738A CN103319738A CN2013102721768A CN201310272176A CN103319738A CN 103319738 A CN103319738 A CN 103319738A CN 2013102721768 A CN2013102721768 A CN 2013102721768A CN 201310272176 A CN201310272176 A CN 201310272176A CN 103319738 A CN103319738 A CN 103319738A
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Abstract
The invention discloses a method for preparing a regenerated cellulose composite membrane by crop straws. The method comprises the following steps of: 1) extracting and refining crop straw cellulose, thus obtaining high-purity straw cellulose slurry; 2) dissolving and regenerating the straw cellulose, namely dispersing the slurry into 5-20 wt percent of NaOH aqueous solution, fully and uniformly stirring the slurry and the solution under the condition of-5-10 DEG C, then adding 5-30 wt percent of urea solution into the mixture, continuously stirring the mixture at the temperature of (-5)-10 DEG C to obtain a homogeneous cellulose solution; and 3) preparing a mixed solution by the cellulose solution and polyvinyl alcohol, and preparing the regenerated cellulose composite membrane by the mixed solution by a tape casting method. According to the method, the crop straws are used as raw materials, and the sodium hydroxide/urea solution is used as a solvent, so that the cost is low, the operation is simple and convenient, the technology is pollution-free, and waste liquid can be used for production fertilizers. The regenerated cellulose composite membrane prepared by the method is high in mechanical property and biodegradability.
Description
Technical field
The invention belongs to agricultural wastes comprehensive utilization and Green Chemistry biological product technical field.What the present invention relates to is to utilize agricultural crop straw to be main raw material, prepares a kind of cellulose membrane by green dissolving cellulos technique, and product possesses good biodegradable character simultaneously.
Background technology
Plant cellulose is natural polymer and the abundantest renewable resources the most ancient on the earth, belongs to environment-friendly material.China is large agricultural country, the agricultural stalk resource that is richly stored with, and at present annual production is more than 800,000,000 tons.As with its fully effectively utilization not only can reduce the greenhouse gas emission protection of the environment, and can alleviate the petrochemical industry resource and increasingly reduce the energy dilemma of bringing.Content of cellulose in the stalk is the abundantest, and the Mierocrystalline cellulose high-efficiency dissolution is made macromolecular material becomes popular in recent years research direction.
On the traditional technology, produce the raw material multiselect cotton fibre that the regenerated celluloses such as glassine paper and artificial silk use, Main Means still is viscose process, typical cellulose viscose manufacturing technique is with Mierocrystalline cellulose and dithiocarbonic anhydride reaction production of cellulose sulfonic acid fat, be dissolved in the sodium hydroxide solution, again solution is ejected in the sulphuric acid soln, thereby the decomposition of Mierocrystalline cellulose sulfonic acid fat has generated again viscose fiber.In actual industrial production, this complex technical process, the costs such as water power are high.The more important thing is that Mierocrystalline cellulose through the repeatedly processing of the chemical reagent such as caustic soda, dithiocarbonic anhydride, has produced a large amount of poison gas and waste water.Thus reason, the once American-European countries of viscose fiber technology prosperity and the Japanese production of having withdrawed from the viscose fiber cellulosic material.
The basic method that solves the regenerated cellulose Sustainable development is to seek green non-poisonous Technology to replace.Select suitable cellulose dissolution system, directly destroy in the cellulosic molecule and the process of intermolecular hydrogen bonding, just becoming the focus of people's research.Paraformaldehyde 96/dimethyl sulfoxide (DMSO) (PF/DMSO) system technique is simple, and solvent toxicity is little, operational safety, but the solvent recuperation difficulty is larger.Ammonium thiocyanate/liquefied ammonia (NH
4SCN/NH
3) the system solvent is nontoxic, but with peptizer during with acid the solvent recuperation difficulty large, the fibre property of producing is general.Lithium chloride/N,N-DIMETHYLACETAMIDE (LiCl/DMAc) reclaims when system uses water as peptizer easily, and the gained fibre property is between common viscose fiber and high wet modulus (HWM) viscose fiber.What current real realization industrialization was produced only has N-methylmorpholine-N-oxide compound (NMMO) system solvent method a kind of, and this system is suitable for dry-wet spinning, processes rear cellulosic traditional HWM viscose fiber that is better than.This system has the good solubility energy, but solvent is expensive, needs effectively to reclaim.The existing NaOH/ aqueous solution of urea of using is as novel dissolving cellulos solvent at present, dissolving cellulos is also successfully prepared the regenerated cellulose fiber/membrane product of better performances, this regenerated cellulose fiber/film cost is lower, but the physical and chemical performance index awaits further raising.
Polyvinyl alcohol (PVA) is that found at present unique has water-soluble and nontoxic superpolymer, and its aqueous solution has well cementability and film-forming properties.The present invention makes membrane product with polyvinyl alcohol composite after adopting friendly process with cheap stalk cellulose dissolving, utilizes hydrogen bond actions a large amount of between Mierocrystalline cellulose and the polyvinyl alcohol molecule in conjunction with the composite membrane of preparation good mechanical performance.This technological process is simple to operate, and uniform in quality is stable, not only has all optics of conventional plastic film and thermodynamic property, and has biodegradability.Cellulose membrane product take glassine paper as representative is looked at because it has the extensive parent that the similar physicals of plastics film has been subject to market, but the product hydrophobic performance is poor, complex manufacturing, and Financial cost is high simultaneously.The present invention wishes to improve and improve the cellulose membrane performance when adopting agricultural crop straw raw material with low cost, finally prepares the cellulose composite membrane of higher quality.
Summary of the invention
The purpose of this invention is to provide the good method for preparing regenerated cellulose composite film of a kind of green, the rapidly dissolvable Mierocrystalline cellulose of the method, the regenerated cellulose composite film good with the polyvinyl alcohol composite processability, easy handling.Product has high tenacity, the characteristics that biodegradable, consistency is good.
Agricultural crop straw of the present invention prepares the method for regenerated cellulose composite film, take agricultural crop straw as raw material, may further comprise the steps:
1) extraction of crop branch fiber element is with refining:
Stalk through shear and dedusting after, 40-60 ℃ of lower microbial fermentation processing 48 hours, to its extruding, corase grind, again in the alkali lye of 0.1%-0.5% concentration 110-130 ℃ boiling 2-3 hour, by discongest with desanding after, obtain high purity stalk cellulose slurry;
2) dissolving of stalk cellulose and regeneration:
Take step 1) slurry that obtains, be scattered in the NaOH aqueous solution of 5-20wt%, under-5-10 ℃ condition, stir, add again the urea soln of 5-30wt%, keep temperature-5-10 ℃ to continue to stir 5-30min, obtain the cellulose solution of homogeneous;
In the above-mentioned cellulose solution, the content of Mierocrystalline cellulose, NaOH and urea is respectively 2-10wt%, 2-10wt% and 2-15wt%;
3) the composite and masking of Mierocrystalline cellulose-polyvinyl alcohol:
With step 2) cellulose solution and the polyvinyl alcohol that obtain make mixing solutions, and mixing solutions is made regenerated cellulose composite film by casting method;
In the above-mentioned regenerated cellulose composite film, the mass ratio of Mierocrystalline cellulose and polyvinyl alcohol is 1: (0.2～2).
Wherein:
Described agricultural crop straw is maize straw or wheat stalk.
Described alkali lye is sodium hydroxide or potassium hydroxide solution.
Step 3) in, the described method for preparing mixing solutions is: first polyvinyl alcohol is mixed with water, 80-90 ℃ of lower the stirring it is fully dissolved, adds again step 2) cellulose solution that obtains, keeps continuing under the 80-90 ℃ of temperature stirring and be cooled to room temperature after 0.5-1 hour; Or,
Cellulose solution is heated to 80-90 ℃ first, directly adds again polyvinyl alcohol, under this temperature, continue to stir 0.5-1.5 hour, then cool to room temperature.
The present invention is take agricultural crop straw as raw material, and sodium hydroxide/aqueous solution of urea is made solvent, and is cheap, simple to operation, and technique is pollution-free, and waste liquid can be used for producing chemical fertilizer.And sodium hydroxide/aqueous solution of urea mixed dissolution system all has preferably solvability to Mierocrystalline celluloses such as maize straw, wheat stalks, has again good mechanical property and biodegradability by the composite membrane that makes with polyvinyl alcohol composite simultaneously.Technique is expected to replace a large amount of uses of the plastics such as present polyethylene, eliminates white pollution, has broad application prospects at packing, child care and material.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1
A kind of agricultural crop straw prepares the method for regenerated cellulose composite film, take maize straw as raw material, may further comprise the steps:
1) maize straw through shear and dedusting after, 50 ℃ of lower microbial fermentations processing 48 hours, to its extruding, corase grind, again 115 ℃ of boilings 3 hours in the sodium hydroxide solution of 0.3% concentration, by discongest with desanding after obtain the maize straw natural color pulp;
2) take maize straw over dry natural color pulp 4g, be scattered in 5 ℃ the NaOH aqueous solution of 25ml15wt%, stir.And then the urea soln of adding 25ml10wt%, keep said temperature, obtain the cellulose solution of stable homogeneous after magnetic agitation is abundant;
3) getting in addition the 2g polyvinyl alcohol mixes with 25ml water, 90 ℃ of lower stirrings until fully dissolving, again with step 2) cellulose solution that obtains mixing and stirring with it, be cooled to room temperature after curtain coating after air-dry a few hours on the flat board, can obtain regenerated cellulose composite film.
Embodiment 2
A kind of agricultural crop straw prepares the method for regenerated cellulose composite film, take wheat stalk as raw material, may further comprise the steps:
1) wheat stalk through shear and dedusting after, 60 ℃ of lower microbial fermentations processing 48 hours, to its extruding, corase grind, again 125 ℃ of boilings 2.5 hours in the sodium hydroxide solution of 0.4% concentration, by discongest with desanding after obtain the wheat stalk natural color pulp;
2) take 1.5g wheat stalk true qualities oven dry stock, stir with the NaOH aqueous solution of 0 ℃ 25ml15wt%, add the urea soln of 25ml20wt% again, magnetic agitation obtains the cellulose solution of oyster white homogeneous after 30 minutes;
3) with step 2) after the cellulose solution that obtains is heated to 80 ℃, directly add the 1.5g polyvinyl alcohol, under this temperature, continue to stir 1 hour fully dissolving mix, be cooled to room temperature after curtain coating on sheet glass, can obtain regenerated cellulose composite film after 2 hours.
Embodiment 3
A kind of agricultural crop straw prepares the method for regenerated cellulose composite film, take wheat stalk as raw material, may further comprise the steps:
1) wheat stalk through shear and dedusting after, 40 ℃ of lower microbial fermentations processing 48 hours, to its extruding, corase grind, again 130 ℃ of boilings 2 hours in the sodium hydroxide solution of 0.5% concentration, by discongest with desanding after obtain the wheat stalk natural color pulp;
2) take 1.5g wheat stalk true qualities oven dry stock, stir with the NaOH aqueous solution of-5 ℃ 10ml5wt%, add the urea soln of 15ml5wt% again, magnetic agitation obtains the cellulose solution of oyster white homogeneous after 30 minutes;
3) with step 2) after the cellulose solution that obtains is heated to 80 ℃, directly add the 0.3g polyvinyl alcohol, under this temperature, continue to stir 1 hour fully dissolving mix, be cooled to room temperature after curtain coating on sheet glass, can obtain regenerated cellulose composite film after 2 hours.
Embodiment 4
A kind of agricultural crop straw prepares the method for regenerated cellulose composite film, take maize straw as raw material, may further comprise the steps:
1) maize straw through shear and dedusting after, 55 ℃ of lower microbial fermentations processing 48 hours, to its extruding, corase grind, again 110 ℃ of boilings 3 hours in the sodium hydroxide solution of 0.1% concentration, by discongest with desanding after obtain the maize straw natural color pulp;
2) take maize straw over dry natural color pulp 3g, be scattered in 10 ℃ the NaOH aqueous solution of 25ml20wt%, stir.And then the urea soln of adding 25ml30wt%, keep said temperature, obtain the cellulose solution of stable homogeneous after magnetic agitation is abundant;
3) getting in addition the 6g polyvinyl alcohol mixes with 25ml water, 80 ℃ of lower stirrings until fully dissolving, again with step 2) cellulose solution that obtains mixing and stirring with it, be cooled to room temperature after curtain coating after air-dry a few hours on the flat board, can obtain regenerated cellulose composite film.
Embodiment 5
A kind of agricultural crop straw prepares the method for regenerated cellulose composite film, take maize straw as raw material, may further comprise the steps:
1) the corn stalk fiber element is extracted with refining, obtain maize straw over dry natural color pulp;
2) get above-mentioned slurry 2g, be scattered in temperature and be in 5 ℃ the NaOH aqueous solution of 15g10wt%, add again the urea soln of 10g15wt%, keep 5 ℃ of temperature to stir 20min, obtain the cellulose solution of homogeneous;
3) with step 2) after the cellulose solution that obtains is heated to 85 ℃, directly add the 3g polyvinyl alcohol, under this temperature, continue to stir 40min and dissolve mixing fully, be cooled to room temperature after curtain coating on sheet glass, can obtain regenerated cellulose composite film after 2 hours.
Embodiment 6
The present invention prepares the method for regenerated cellulose composite film, take wheat stalk as raw material, may further comprise the steps:
1) the wheat stalk Mierocrystalline cellulose is extracted with refining, obtain wheat stalk over dry natural color pulp;
2) get above-mentioned over dry natural color pulp 2g, be scattered in temperature and be in 5 ℃ the NaOH aqueous solution of 20g15wt%, add again the urea soln of 20g10wt%, keep 5 ℃ of temperature to stir 20min, obtain the cellulose solution of homogeneous;
3) with step 2) after the cellulose solution that obtains is heated to 85 ℃, directly add the 0.8g polyvinyl alcohol, under this temperature, continue to stir 40min and dissolve mixing fully, be cooled to room temperature after curtain coating on sheet glass, can obtain regenerated cellulose composite film after 2 hours.
Claims (5)
1. an agricultural crop straw prepares the method for regenerated cellulose composite film, it is characterized in that, may further comprise the steps:
1) the crop branch fiber element is extracted with refining, obtain high purity stalk cellulose slurry;
2) with step 1) slurry that obtains, be scattered in the NaOH aqueous solution of 5-20wt%, under-5-10 ℃ condition, stir, add again the urea soln of 5-30wt%, keep temperature-5-10 ℃ to continue to stir 5-30min, obtain the cellulose solution of homogeneous;
In the described cellulose solution, the content of Mierocrystalline cellulose, NaOH and urea is respectively 2-10wt%, 2-10wt% and 2-15wt%;
3) with step 2) cellulose solution and the polyvinyl alcohol that obtain make mixing solutions, and mixing solutions is made regenerated cellulose composite film by casting method;
In the described regenerated cellulose composite film, the mass ratio of Mierocrystalline cellulose and polyvinyl alcohol is 1: (0.2～2).
2. agricultural crop straw according to claim 1 prepares the method for regenerated cellulose composite film, it is characterized in that, described agricultural crop straw is maize straw or wheat stalk.
3. agricultural crop straw according to claim 1 prepares the method for regenerated cellulose composite film, it is characterized in that, step 1) in, the extraction of stalk cellulose and process for purification are: stalk is through shearing and dedusting, processed 48 hours at 40-60 ℃ of lower microbial fermentation, to its extruding, corase grind, again in the alkali lye of 0.1%-0.5% concentration 110-130 ℃ boiling 2-3 hour, and then discongest and desanding.
4. agricultural crop straw according to claim 3 prepares the method for regenerated cellulose composite film, it is characterized in that step 1) in, described alkali lye is sodium hydroxide or potassium hydroxide solution.
5. agricultural crop straw according to claim 1 prepares the method for regenerated cellulose composite film, it is characterized in that, step 3) in, the method for preparing mixing solutions is: first polyvinyl alcohol is mixed with water, being heated to 80-90 ℃ of stirring fully dissolves it, add again step 2) cellulose solution that obtains, keep continuing under the 80-90 ℃ of temperature to stir after 0.5-1 hour to be cooled to room temperature; Or,
Cellulose solution is heated to 80-90 ℃ first, directly adds again polyvinyl alcohol, keep this temperature to continue to stir 0.5-1.5 hour, then cool to room temperature.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104017243A (en) * | 2014-05-26 | 2014-09-03 | 北京印刷学院 | Completely degradable antibacterial fresh-keeping packaging material based on natural cellulose and preparation method thereof |
| CN104028235A (en) * | 2014-06-01 | 2014-09-10 | 吴涛 | Barley straw adsorbing material and preparation method thereof |
| CN104028230A (en) * | 2014-06-01 | 2014-09-10 | 李�荣 | Novel sorghum straw adsorbing material and preparation method thereof |
| CN105131317A (en) * | 2015-09-17 | 2015-12-09 | 华南理工大学 | Composite hydrogel membrane, method for preparing hydrogel membrane from bamboo shoot residues and application |
| CN110468614A (en) * | 2019-07-09 | 2019-11-19 | 仲恺农业工程学院 | A kind of preparation method and applications of cellulose membrane |
| CN111057272A (en) * | 2019-11-20 | 2020-04-24 | 湖南工业大学 | Fully-degradable cellulose-reinforced PVA composite material and preparation method thereof |
| CN116444865A (en) * | 2023-03-28 | 2023-07-18 | 珠海科技学院 | Breathable preservative film and preparation method thereof |
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| CN101712805A (en) * | 2009-11-06 | 2010-05-26 | 北京化工大学 | Method for preparing degradable mulch by reusing organic waste residues of biomass |
| CN101735420A (en) * | 2008-11-20 | 2010-06-16 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method and application method of biomass liquid agricultural membrane material |
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| CN101323706A (en) * | 2008-07-25 | 2008-12-17 | 王芝代 | Biodegradable liquid agricultural film |
| CN101735420A (en) * | 2008-11-20 | 2010-06-16 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method and application method of biomass liquid agricultural membrane material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017243A (en) * | 2014-05-26 | 2014-09-03 | 北京印刷学院 | Completely degradable antibacterial fresh-keeping packaging material based on natural cellulose and preparation method thereof |
| CN104028235A (en) * | 2014-06-01 | 2014-09-10 | 吴涛 | Barley straw adsorbing material and preparation method thereof |
| CN104028230A (en) * | 2014-06-01 | 2014-09-10 | 李�荣 | Novel sorghum straw adsorbing material and preparation method thereof |
| CN105131317A (en) * | 2015-09-17 | 2015-12-09 | 华南理工大学 | Composite hydrogel membrane, method for preparing hydrogel membrane from bamboo shoot residues and application |
| CN105131317B (en) * | 2015-09-17 | 2018-06-29 | 华南理工大学 | Compound water congealing glued membrane and bamboo shoots leftover bits and pieces prepare method and the application of the aquagel membrane |
| CN110468614A (en) * | 2019-07-09 | 2019-11-19 | 仲恺农业工程学院 | A kind of preparation method and applications of cellulose membrane |
| CN110468614B (en) * | 2019-07-09 | 2021-12-10 | 仲恺农业工程学院 | Preparation method and application of cellulose membrane |
| CN111057272A (en) * | 2019-11-20 | 2020-04-24 | 湖南工业大学 | Fully-degradable cellulose-reinforced PVA composite material and preparation method thereof |
| CN116444865A (en) * | 2023-03-28 | 2023-07-18 | 珠海科技学院 | Breathable preservative film and preparation method thereof |
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