CN1112396C - Cellulose film preparing method - Google Patents
Cellulose film preparing method Download PDFInfo
- Publication number
- CN1112396C CN1112396C CN00114485A CN00114485A CN1112396C CN 1112396 C CN1112396 C CN 1112396C CN 00114485 A CN00114485 A CN 00114485A CN 00114485 A CN00114485 A CN 00114485A CN 1112396 C CN1112396 C CN 1112396C
- Authority
- CN
- China
- Prior art keywords
- cellulose
- water solution
- aqueous solution
- solvent
- materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention discloses a preparation method of a cellulose membrane. In the method, cellulose is dissolved at the temperature of 0 to 10DEG C by adopting a mixed water solution of 4 to 8% of sodium hydroxide and 2 to 8% of urea as a solvent, and a coagulating agent in use is a CaCl2 water solution, an HCl water solution or an acetic acid water solution. The method has the advantages of no pollution and low cost. The method can be used for dissolving various kinds of cellulose slurry with the viscosity-average molecular weight of lower than 8.5*10<4>. The prepared cellulose membrane has the advantages of favorable light transmitting property, favorable mechanical performance and favorable biodegradability. The prepared cellulose membrane can be used for nursing materials, covering materials, packaging materials and separating materials in the fields of agriculture, chemical industry, foods and environments.
Description
The present invention relates to a kind of preparation method of cellulose membrane.
Plant cellulose is a renewable resources the abundantest on the earth, belongs to environment-friendly material, makes full use of Mierocrystalline cellulose and not only can protect environment, and can save limited petroleum resources.Mierocrystalline cellulose is made the film after being used for derivatize on a small quantity, and the viscose process that is still of major industryization is produced artificial silk and glassine paper so far, but produces a large amount of CS in the production process
2And serious environment pollution.In addition, have nearly 50 years history with cuprammonium process production of cellulose silk and non-woven fabrics in company of Japanese Asahi Chemical Industry.But the equipment of solvent recuperation and recycle and expense are expensive.N-methyl-N-morpholine oxide is the strongest up to now cellosolve, comes into the market with the plain product of the small amount of fibers of its preparation, as the commodity Tencel (1989 years) of Austrian commodity Lyocell (nineteen ninety) and Britain.But owing to it costs an arm and a leg, spinning temperature is higher, the suitability for industrialized production slower development.The NaOH aqueous solution (K.Kamide, etal, Japan Patent 1777283,1983) is the most cheap solvent of dissolving cellulos.The Mierocrystalline cellulose (its intermolecular hydrogen bonding is corrupted to a certain degree) that Japan Asahi Chemical Industry company will steam after quick-fried is dissolved in when 4 ℃ of left and right sides in the NaOH aqueous solution of 7～9wt%, and spray is thread after 20～70%H
2SO
4Aqueous solution regeneration product (SEN ' I GAKKAISHI, 52,7,1996).But this solvent only can dissolve viscosity-average molecular weight M
ηLess than 4 * 10
4Cellulosic molecule, and obtained fiber yarn transparency and intensity are lower, are not suitable for industrialization spinning or curtain coating legal system film.
The preparation method who the purpose of this invention is to provide a kind of cellulose membrane, employing is pollution-free in this method, cost is low, can dissolve the bigger cellulosic mixed solvent of viscosity-average molecular weight, and the regenerated cellulose film of preparation is answered tool good light transmittance and mechanical property.
For achieving the above object, scheme of the present invention is as follows:
A kind of method for preparing cellulose membrane in solvent, fully stirs cellulose dissolution, makes cellulose solution, with cellulose solution knifing onboard, solidifies afterwash with peptizer and is drying to obtain regenerated cellulose film again.Temperature during cellulose dissolution is 0～10 ℃, and used solvent is for containing the mixed aqueous solution of 4～8% (weight percent) sodium hydroxide and 2～8% urea.The mixed solvent of making can be preserved standby in refrigerator.In the time of 0～10 ℃, this mixed solvent is to viscosity-average molecular weight M
ηLess than 8.5 * 10
4Natural cellulose slurry and M
ηLess than 12 * 10
4Regenerated cellulose and the wood pulp cellulose that steams after quick-fried have optimal dissolution.
With natural cellulose (M
η＜8.5 * 10
4) or regenerated cellulose and steam wood pulp cellulose (M after quick-fried
η＜12 * 10
4) be dispersed in the above-mentioned mixed solvent, in ice-water bath, stirred 5 minutes freezing then (0～10 ℃) 30 minutes to 12 hours.Take out the back and under room temperature, fully stir, promptly make transparent cellulose solution.It is back with casting method knifing on sheet glass that above-mentioned transparent cellulose solution is filtered, outgases.With this film 5wt%CaCl
2The aqueous solution handled 1～10 minute, the washing back was immersed in 1～2wt%HCl aqueous solution 1～5 minute, clean dry promptly gets regenerated cellulose film.System as peptizer also has 5wt%CaCl
2/ 1～2wt%HCl mixed aqueous solution, 1～2wt%HCl aqueous solution, 1-2mol/L aqueous acetic acid etc.
The present invention makes solvent with sodium hydroxide/aqueous solution of urea, and low price is simple to operation, and is pollution-free, and waste liquid can be used for chemical fertilizers production.The Mierocrystalline cellulose that this mixed solvent is bigger to viscosity-average molecular weight (cotton linter pulp, straw fiber slurry, bagasse pulp, wood pulp and cellulosic nonwoven fabric and steam quick-fried cellulose slurry etc.) has bigger solvability, especially for wood pulp cellulose behind the steam explosion and regenerated cellulose.Good, the tool excellent mechanical property of regenerated cellulose film light transmission and the biodegradability of preparation, be expected to replace prescription and the technology that present viscose process is produced glassine paper and artificial silk, and on child care, covering, packing and parting material, have a wide range of applications.Used peptizer is CaCl in the method
2The aqueous solution, the HCl aqueous solution or aqueous acetic acid, low price, production process are simple, convenient, nontoxic, harmless, pollution-free, safe.
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
Get cotton linters cellulose slurry (viscosity-average molecular weight M
η=8.4 * 10
4) 10 grams, add 200 gram 6wt%NaOH/8wt% urea mixed aqueous solutions, in ice-water bath below 6 ℃, stirred 5 minutes, be placed in the refrigerator (0 ℃) then freezing 3 hours, take out fully to stir and obtain colourless transparent solution.Remove by filter on a small quantity not behind the fibrinolysin knifing on sheet glass, put into the 2mol/L aqueous acetic acid immediately, soak after 2 minutes and take out, water is rinsed well.Be attached at last to dry naturally on the sheet glass and obtain regenerated cellulose film.Record its tensile strength σ by electronic tension tester
b, elongation at break ε
bAnd Young's modulus is respectively 57MPa, 10% and 2515MPa.
Embodiment 2
(making viscosity-average molecular weight in 16 hours with the clorox degraded is 1.8 * 10 to get 10g cotton linters cellulose slurry
4Mierocrystalline cellulose), add 190 gram 6wt%NaOH/4wt% urea mixed aqueous solutions then, in ice-water bath below 6 ℃, stirred 5 minutes, be placed in the refrigerator (0 ℃) then freezing 3 hours.Take out fully to stir and obtain colourless transparent solution, directly knifing on sheet glass.In the 2mol/L aqueous acetic acid, soaked 5 minutes then, then at 5%H
2SO
4The middle immersion 2 minutes after taking-up washes, dried on sheet glass naturally, obtains transparent regenerated cellulose film.Record its tensile strength σ
b, elongation at break ε
bBe respectively 57MPa, 8%, transmittance is 87% (400～800nm).
Embodiment 3
Get 10 gram cuprammonium regenerated cellulose non-woven fabrics (viscosity-average molecular weight M
η=11.2 * 10
4) be dissolved in as stated above in the 250mL 6wt%NaOH/4wt% urea mixed aqueous solution, after stirring, filter, outgasing, knifing on clean sheet glass places 5wt%CaCl immediately
2Solidify regeneration 5 minutes in the aqueous solution, wash with water after the taking-up and totally obtain transparent regenerated cellulose film,, wash with water at last totally, dry again with handling 2 minutes in the 1.3wt%HCl aqueous solution.The tensile strength of gained regenerated cellulose film, elongation at break and Young's modulus are respectively 88.7MPa and 11.3% and 3733MPa, and transmittance is 90% (400～800nm).
Claims (3)
1. method for preparing cellulose membrane, with cellulose dissolution in solvent, fully stir, make cellulose solution, again with cellulose solution knifing onboard, solidify afterwash with peptizer and be drying to obtain regenerated cellulose film, it is characterized in that: the temperature during cellulose dissolution is 0～10 ℃, and used solvent is the mixed aqueous solution that the urea of the sodium hydroxide and 2～8% (weight) of 4～8% (weight) is formed.
2. method according to claim 1 is characterized in that: described Mierocrystalline cellulose is viscosity-average molecular weight M
ηLess than 8.5 * 10
4Natural cellulose slurry, M
ηLess than being 2 * 10
4Regenerated cellulose or steam wood pulp cellulose after quick-fried.
3. method according to claim 1 is characterized in that: described peptizer is CaCl
2The aqueous solution, the HCl aqueous solution or aqueous acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00114485A CN1112396C (en) | 2000-04-17 | 2000-04-17 | Cellulose film preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00114485A CN1112396C (en) | 2000-04-17 | 2000-04-17 | Cellulose film preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1318582A CN1318582A (en) | 2001-10-24 |
| CN1112396C true CN1112396C (en) | 2003-06-25 |
Family
ID=4584161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00114485A Expired - Fee Related CN1112396C (en) | 2000-04-17 | 2000-04-17 | Cellulose film preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1112396C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300227C (en) * | 2005-05-30 | 2007-02-14 | 武汉大学 | Microporous membrane and its preparing process and use thereof |
| CN1851462B (en) * | 2006-05-18 | 2010-12-08 | 浙江大学 | Method for preparing network-like macroporous structure cellolose adsorption and transfer membrane |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282773C (en) | 2005-05-30 | 2006-11-01 | 武汉大学 | Method for preparing regenerative cellulose fiber by two-step coagulating bath process |
| CN1313495C (en) * | 2005-08-24 | 2007-05-02 | 武汉大学 | Hydroxy ethyl cellulose preparation method |
| CN103055347B (en) * | 2013-01-21 | 2014-09-03 | 武汉大学 | Preparation method of cellulose gel material of onion structure |
| CN104629067B (en) * | 2015-02-16 | 2017-10-27 | 东北林业大学 | A kind of preparation method for regenerating the plain composite membrane of polyvinyl alcohol of antibiotic fiber |
| CN105350313B (en) * | 2015-12-24 | 2017-10-03 | 西南大学 | Anti- prodding and itching feeling method for sorting of the sodium hydroxide/urea aqueous systems to ramie fabric |
| CN106012667A (en) * | 2016-05-20 | 2016-10-12 | 广州纽楷美新材料科技有限公司 | Hollocellulose transparent paper and preparation method thereof |
| CN106750439B (en) * | 2017-02-16 | 2020-01-21 | 深圳先进技术研究院 | Method for preparing packaging film by utilizing bagasse and prepared packaging film |
| CN108892795A (en) * | 2018-07-19 | 2018-11-27 | 天津工业大学 | A kind of high strength fibre element film and its preparation method and application |
| CN109694928B (en) * | 2018-12-27 | 2021-10-15 | 广西科技大学 | Method for decoloring sugar solution |
| CN112362202A (en) * | 2020-11-26 | 2021-02-12 | 广东彩乐智能包装科技有限公司 | Paper-based pressure sensor, preparation method thereof, nano cellulose paper and pressure-sensitive sensing piece |
| CN112951481B (en) * | 2021-01-28 | 2022-10-14 | 广东彩乐智能包装科技有限公司 | High-transparency conductive paper and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716038A (en) * | 1980-07-04 | 1982-01-27 | Daicel Chem Ind Ltd | Regenerated cellulose film |
| US4526620A (en) * | 1982-12-08 | 1985-07-02 | Neste Oy | Cellulose carbamate solutions |
| US4530999A (en) * | 1983-11-02 | 1985-07-23 | Neste Oy | Method of producing cellulose carbamate fibers or films |
| JPS60185883A (en) * | 1984-02-29 | 1985-09-21 | Sadao Nishibori | Production of woody floor sheet material |
| CN1061608A (en) * | 1990-11-17 | 1992-06-03 | 武汉大学 | Cotton stalk and Pericarppium arachidis hypogaeae prepare the method for regenerated cellulose film |
-
2000
- 2000-04-17 CN CN00114485A patent/CN1112396C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716038A (en) * | 1980-07-04 | 1982-01-27 | Daicel Chem Ind Ltd | Regenerated cellulose film |
| US4526620A (en) * | 1982-12-08 | 1985-07-02 | Neste Oy | Cellulose carbamate solutions |
| US4530999A (en) * | 1983-11-02 | 1985-07-23 | Neste Oy | Method of producing cellulose carbamate fibers or films |
| JPS60185883A (en) * | 1984-02-29 | 1985-09-21 | Sadao Nishibori | Production of woody floor sheet material |
| CN1061608A (en) * | 1990-11-17 | 1992-06-03 | 武汉大学 | Cotton stalk and Pericarppium arachidis hypogaeae prepare the method for regenerated cellulose film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300227C (en) * | 2005-05-30 | 2007-02-14 | 武汉大学 | Microporous membrane and its preparing process and use thereof |
| CN1851462B (en) * | 2006-05-18 | 2010-12-08 | 浙江大学 | Method for preparing network-like macroporous structure cellolose adsorption and transfer membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1318582A (en) | 2001-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1112396C (en) | Cellulose film preparing method | |
| CN101037479B (en) | Method for dissolving cellulos | |
| JP4679641B2 (en) | Non-toxic processes and systems for pilot scale production of cellulosic products | |
| CN102127241B (en) | Method for preparing plant cellulose film by taking herbaceous plant as raw material | |
| CN101274988A (en) | Industrial method for preparing regenerated cellulose film | |
| CN109402774B (en) | Anti-fibrillation cellulose fiber and preparation method thereof | |
| CN102660791A (en) | Old clothes recovery method | |
| CN1252163C (en) | Lithium hydrate and carbamide composition solvent for dissolving cellulous fiber and its use | |
| CN101275369A (en) | Cellulose-dissolved dissolvant and industrial method thereof | |
| CN101130605A (en) | Solvent composition for solubilizing cellulose | |
| CN114395916B (en) | Antigen fibrillated cellulose fiber and preparation method thereof | |
| CN1125845C (en) | Solvent composition and its use | |
| CN104262642A (en) | Method for dissolving cellulose in aqueous solution of NaOH/thiourea at normal temperature | |
| CN101074285B (en) | Method for dissolving cellulose | |
| CN1235962C (en) | Solvent for solving cellulose and its application | |
| CN101168602B (en) | Corn protein/cellulose mixed solution, and preparation method and use thereof | |
| CN1126760C (en) | Cellulose dissolved thiourea alkaline liquod solvent and method for preparing regenerated fibrous membrane | |
| CN1193061C (en) | Solvent composite and preparation method and use thereof | |
| CN101555321A (en) | Solvent composition and preparation method and application thereof | |
| CN1229214C (en) | Process for preparing regenerated cellulose films and wires | |
| CN100572423C (en) | A kind of method of dissolving cellulos | |
| CN1289587C (en) | Cellosolve and its use | |
| CN101168603A (en) | Soybean separation protein/cellulose mixed solution, and preparation method and use thereof | |
| CN102704038A (en) | Cyanoethyl chitosan fiber and preparation method thereof | |
| CN107304246A (en) | A kind of solvent for dissolving cellulose and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |