CN101168602A - Corn protein/cellulose mixed solution, and preparation method and use thereof - Google Patents
Corn protein/cellulose mixed solution, and preparation method and use thereof Download PDFInfo
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- CN101168602A CN101168602A CNA2007101685203A CN200710168520A CN101168602A CN 101168602 A CN101168602 A CN 101168602A CN A2007101685203 A CNA2007101685203 A CN A2007101685203A CN 200710168520 A CN200710168520 A CN 200710168520A CN 101168602 A CN101168602 A CN 101168602A
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Abstract
The invention discloses zein/cellulose mixed solution. Zein is dispersed in combined water solution including 6 to 8 wt percent of NaOH and 10 to 14 wt percent of urea, the solution is stirred uniformly under the room temperature to obtain 0.5 to 5 wt percent of zein solution, and then the prepared zein solution is precooled to -12 to -13 DEG C, cellulose is added into the zein solution, and the solution is stirred uniformly to obtain the transparent zein/cellulose mixed solution; wherein, according to the weight ratio, the proportion of the zein and the cellulose is 0.5:9.5 to 5:5, the zein and the cellulose account for 4 to 8 wt percent of the mixed solution, and the rest is the combined water solution of NaOH/urea. Or the cellulose is directly dissolved with mixed water solution precooled to -12 to -13 DEG C and composed of NaOH, urea, and zein to obtain the zein/cellulose mixed solution. The obtained mixed solution can prepare zein/cellulose membranes, fiber, and other composite materials through casting film forming and other methods.
Description
Technical field
The present invention relates to a kind of zein/cellulose mixed solution and its production and use.
Background technology
Plant cellulose is a renewable resources the abundantest on the earth, and zein is the same with Mierocrystalline cellulose, belongs to environment-friendly material, and the source is also very extensive.Make full use of Semen Maydis cellulose and protein and not only can protect environment, and can save limited petroleum resources.Particularly protein fibre development recently is rapider, plurality of advantages as softness, moisture absorption, ventilative, do not produce static etc. and make it enjoy favor, but simultaneously also because its finished product price comparison costliness, physicalies such as wear resistance, dyeability are bad and its production application is limited to.Zein/cellulose composite material then can make bill of material reveal more excellent performance in conjunction with both advantages.Existing complex method is to use the viscose process dissolving cellulos, with the protein soln blend, makes film and fiber and other material more then, and not only there is pollution in this technology, and can cause protein seriously to run off in the operation of desulfurization.
Summary of the invention
The purpose of this invention is to provide a kind of zein/cellulose mixed solution and its production and use, this method is mixing protein and Mierocrystalline cellulose uniformly, and it is simple to solidify technological process such as regeneration, need not desulfurization, whole technological process is pollution-free, and the protein stream vector is few, is easy to industrialization.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of zein/cellulose mixed solution is made up of the combination solution of zein, Mierocrystalline cellulose and NaOH/ urea; The combination solution of NaOH/ urea is made of the water of 6～8wt%NaOH, 10～14wt% urea and surplus; Wherein, zein and cellulosic weight ratio are: 0.5: 9.5～5: 5, and 4～8wt% of zein and cellulose comprises mixing solutions, all the other are the combination solution of NaOH/ urea.
The preparation method of above-mentioned zein/cellulose mixed solution, zein is scattered in the combination solution that contains 6～8wt%NaOH and 10～14wt% urea, at room temperature stir and obtain 0.5～5wt% corn protein solution, the corn protein solution that makes is pre-chilled to-12～-13 ℃ then, add Mierocrystalline cellulose, stirring to obtain transparent zein/cellulose mixed solution; Wherein by weight, zein and cellulosic ratio are: 0.5: 9.5～5: 5, and 4～8wt% of zein and cellulose comprises mixing solutions, all the other are the combination solution of NaOH/ urea.
The preparation method of above-mentioned zein/cellulose mixed solution is scattered in zein in the combination solution that contains 6～8wt%NaOH and 10～14wt% urea, and at room temperature stirring obtains 10～40wt% corn protein solution; The combination solution that will contain 6～8wt%NaOH and 10～14 wt% urea is pre-chilled to-12～-13 ℃, adds Mierocrystalline cellulose, and stirring obtains cellulose solution; The corn protein solution and the cellulose solution that make are respectively mixed, can obtain transparent zein/cellulose mixed solution.Wherein by weight, zein and cellulosic ratio are: 0.5: 9.5～5: 5, and 4～8wt% of zein and cellulose comprises mixing solutions, all the other are the combination solution of NaOH/ urea.
A kind of method of utilizing above-mentioned zein/cellulose mixed solution to prepare zein/cellulose composite membrane, with zein/cellulose mixed solution curtain coating, through containing the precipitation bath solidification forming of sulfuric acid or sulfuric acid/sodium sulfate, can obtain zein/cellulose composite membrane after the drying, wherein Mierocrystalline cellulose is 9.5: 0.5～5: 5 with the dry weight ratio of zein.
A kind of method of utilizing above-mentioned zein/cellulose mixed solution to prepare zein/cellulose composite fiber, adopt wet-spinning, with zein/cellulose mixed solution spray silk, through containing the precipitation bath solidification forming of sulfuric acid or sulfuric acid/sodium sulfate, can obtain zein/cellulose composite fiber after the drying, wherein the dry weight of Mierocrystalline cellulose and zein is 9.5: 0.5～5: 5.
Compared with the prior art, innovation of the present invention is as follows:
Zein and cellulosic dissolving, blend and regeneration all are physical processes among the present invention, and chemical reaction does not take place.Wherein, blending technology both can adopt zein and Mierocrystalline cellulose to dissolve solution blending afterwards respectively, also can adopt the direct dissolving cellulos of proteinaceous solution and blend.Whole technology is not high to equipment requirements, need not desulfurization, and the zein number of dropouts is few, helps suitability for industrialized production, the easy recycling use of waste liquid.The present invention is a raw material with sodium hydroxide, urea, water, and low price is simple to operation, environmentally safe.
Embodiment
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
0.5 gram zein is scattered in 190 grams contains in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stir, be chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately until the zein dissolving
η=8 * 10
4) 9.5 grams drop into wherein, stir (about 3 minutes) under 0 ℃, can make zein/cellulose mixed solution.Wherein Mierocrystalline cellulose is 9.5: 0.5 with proteinic dry weight ratio, and Mierocrystalline cellulose and protein close and accounts for 5% of solution.
Embodiment 2
4 gram zeins are scattered in 192 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stir, be chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately until the zein dissolving
η=10 * 10
4) 4 grams drop into wherein, stir (about 3 minutes) under 0 ℃, can make zein/cellulose mixed solution.Wherein Mierocrystalline cellulose is 5: 5 with proteinic dry weight ratio, and Mierocrystalline cellulose and protein close and accounts for 4% of solution.
Embodiment 3
6 gram zeins are scattered in 184 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stir, be chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately until the zein dissolving
η=6 * 10
4) 10 grams drop into wherein, stir (about 3 minutes) under 0 ℃, can make zein/cellulose mixed solution.Wherein Mierocrystalline cellulose is 3: 5 with proteinic dry weight ratio, and Mierocrystalline cellulose and protein close and accounts for 8% of solution.
Embodiment 4
0.5 gram zein is scattered in 10 grams contains in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stirring makes corn protein solution.180 gram 7wt%NaOH/12wt% aqueous solution of urea are chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately
η=8 * 10
4) 9.5 grams drop into wherein, stir (about 3 minutes) under 0 ℃, make transparent cellulose solution.Above-mentioned corn protein solution and cellulose solution are mixed, stir 30min, can make zein/cellulose mixed solution.Wherein Mierocrystalline cellulose is 9.5: 0.5 with proteinic dry weight ratio, and Mierocrystalline cellulose and protein close and accounts for 5% of solution.
Embodiment 5
6 gram zeins are scattered in 30 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stirring makes corn protein solution.154 gram 7wt%NaOH/12wt% aqueous solution of urea are chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately
η=6 * 10
4) 10 grams drop into wherein, stir (about 3 minutes) under 0 ℃, make transparent cellulose solution.Above-mentioned corn protein solution and cellulose solution are mixed, stir 30min, can make zein/cellulose mixed solution.Wherein Mierocrystalline cellulose is 3: 5 with proteinic dry weight ratio, and Mierocrystalline cellulose and protein close and accounts for 8% of solution.
Embodiment 6
4 gram zeins are scattered in 30 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stirring makes corn protein solution.162 gram 7wt%NaOH/12wt% aqueous solution of urea are chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately
η=8 * 10
4) 4 grams drop into wherein, stir (about 3 minutes) under 0 ℃, make transparent cellulose solution.Above-mentioned corn protein solution and cellulose solution are mixed, stir 30min, can make zein/cellulose mixed solution.Wherein Mierocrystalline cellulose is 5: 5 with proteinic dry weight ratio, and Mierocrystalline cellulose and protein close and accounts for 4% of solution.
Embodiment 7
1 gram zein is scattered in 200 grams contains in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stir, be chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately until the zein dissolving
η=10 * 10
4) 9 grams drop into wherein, stir (about 3 minutes) under 0 ℃, can make zein/cellulose mixed solution.The zein that makes/cellulose solution is filtered after the deaeration casting film-forming on sheet glass, put into the 5wt% aqueous sulfuric acid then, soak after 5 minutes and take out, water is rinsed well, dry, can obtain zein/cellulose composite membrane, wherein Mierocrystalline cellulose is 9: 1 with proteinic dry weight ratio.Record its tensile strength σ by electronics pulling experiment machine
b, elongation at break ε
bAnd Young's modulus is respectively 110MPa, 10% and 5000MPa, and transmittance is 89% (800nm), finally records the zein number of dropouts less than 5%.Perhaps zein/cellulose solution is carried out wet-spinning, can obtain zein/cellulose composite fiber.
Embodiment 8
3 gram zeins are scattered in 27 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stirring to make 10% corn protein solution.193 gram 7wt%NaOH/12wt% aqueous solution of urea are chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately
η=10 * 10
4) 7 grams drop into wherein, stir (about 3 minutes) under 0 ℃, make transparent cellulose solution.Above-mentioned 30 gram corn protein solutions and 200 gram cellulose solutions are mixed, stir 30min, filter deaeration, casting film-forming, water is rinsed well, dries, and can obtain zein/cellulose composite membrane, and wherein Mierocrystalline cellulose is 7: 3 with proteinic dry weight ratio.Record its tensile strength σ by electronics pulling experiment machine
b, elongation at break ε
bAnd Young's modulus is respectively 90MPa, 7% and 5500MPa, and transmittance is 78% (800nm), finally records the zein number of dropouts less than 20%.Perhaps zein/cellulose solution is carried out wet-spinning, can make zein/cellulose composite fiber.
Embodiment 9
4 gram zeins are scattered in 200 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～14wt% urea, at room temperature stir, be chilled to-12 ℃ in advance, get cotton linter pulp (viscosity-average molecular weight M immediately until the zein dissolving
η=10 * 10
4) 6 grams drop into wherein, stir (about 3 minutes) under 0 ℃, can make zein/cellulose mixed solution.The zein that makes/cellulose solution is filtered after the deaeration casting film-forming on sheet glass, put into the 5wt% aqueous sulfuric acid then, soak after 5 minutes and take out, water is rinsed well, dry, can obtain zein/cellulose composite membrane, wherein Mierocrystalline cellulose is 6: 4 with proteinic dry weight ratio.Record its tensile strength σ by electronics pulling experiment machine
b, elongation at break ε
bReach Young's modulus and be respectively 86MPa, 6% and 5200 MPa, transmittance is 75% (800nm), finally records the zein number of dropouts less than 25%.Perhaps zein/cellulose solution is carried out wet-spinning, can obtain zein/cellulose composite fiber.
Claims (5)
1. a zein/cellulose mixed solution is made up of the combination solution of zein, Mierocrystalline cellulose and NaOH/ urea; The combination solution of NaOH/ urea is made of the water of 6～8wt%NaOH, 10～14wt% urea and surplus; Wherein, zein and cellulosic weight ratio are: 0.5: 9.5～5: 5, and 4～8wt% of zein and cellulose comprises mixing solutions, all the other are the combination solution of NaOH/ urea.
2. the preparation method of the described zein/cellulose mixed solution of claim 1, zein is scattered in the combination solution that contains 6～8wt%NaOH and 10～14wt% urea, at room temperature stir and obtain 0.5～5wt% corn protein solution, the corn protein solution that makes is pre-chilled to-12～-13 ℃ then, add Mierocrystalline cellulose, stir and promptly obtain transparent zein/cellulose mixed solution; Wherein by weight, zein and cellulosic ratio are: 0.5: 9.5～5: 5, and 4～8wt% of zein and cellulose comprises mixing solutions, all the other are the combination solution of NaOH/ urea.
3. the preparation method of the described zein/cellulose mixed solution of claim 1 is scattered in zein in the combination solution that contains 6～8wt%NaOH and 10～14wt% urea, and at room temperature stirring obtains 10～40wt% corn protein solution; The combination solution that will contain 6～8wt%NaOH and 10～14wt% urea is pre-chilled to-12～-13 ℃, adds Mierocrystalline cellulose, and stirring obtains cellulose solution; The corn protein solution and the cellulose solution that make are respectively mixed, promptly obtain transparent zein/cellulose mixed solution.Wherein by weight, zein and cellulosic ratio are: 0.5: 9.5～5: 5, and 4～8wt% of zein and cellulose comprises mixing solutions, all the other are the combination solution of NaOH/ urea.
4. utilize the described zein/cellulose mixed solution of claim 1 to prepare the method for zein/cellulose composite membrane, with zein/cellulose mixed solution curtain coating, through containing the precipitation bath solidification forming of sulfuric acid or sulfuric acid/sodium sulfate, can obtain zein/cellulose composite membrane after the drying, wherein Mierocrystalline cellulose is 9.5: 0.5～5: 5 with the dry weight ratio of zein.
5. utilize the described zein/cellulose mixed solution of claim 1 to prepare the method for zein/cellulose composite fiber, adopt wet-spinning, with zein/cellulose mixed solution spray silk, through containing the precipitation bath solidification forming of sulfuric acid or sulfuric acid/sodium sulfate, can obtain zein/cellulose composite fiber after the drying, wherein Mierocrystalline cellulose is 9.5: 0.5～5: 5 with proteinic dry weight ratio.
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| CN2007101685203A CN101168602B (en) | 2007-11-29 | 2007-11-29 | Corn protein/cellulose mixed solution, and preparation method and use thereof |
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| CN2007101685203A CN101168602B (en) | 2007-11-29 | 2007-11-29 | Corn protein/cellulose mixed solution, and preparation method and use thereof |
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| CN101168602A true CN101168602A (en) | 2008-04-30 |
| CN101168602B CN101168602B (en) | 2010-09-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851428A (en) * | 2010-06-10 | 2010-10-06 | 西安石油大学 | Lignin-polysaccharide composite material product and preparation method thereof |
| CN102677222A (en) * | 2012-06-06 | 2012-09-19 | 武汉纺织大学 | Preparation method of high-strength cellulose protein fibers |
| CN102677221A (en) * | 2012-06-04 | 2012-09-19 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN104004209A (en) * | 2014-06-13 | 2014-08-27 | 东华大学 | Method for preparing polycaprolactone-keratin composite membranes |
| US11840585B2 (en) | 2017-05-05 | 2023-12-12 | Betulium Oy | Cellulose derivatives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168767C (en) * | 2002-07-09 | 2004-09-29 | 武汉大学 | Prepn. process of intermingled chitin/cellulose material in sodium hydroxide/urea water solution system |
| CN100500690C (en) * | 2007-03-27 | 2009-06-17 | 北京赛特瑞科技发展有限公司 | Soluble maize protein, its preparing method and use |
-
2007
- 2007-11-29 CN CN2007101685203A patent/CN101168602B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851428A (en) * | 2010-06-10 | 2010-10-06 | 西安石油大学 | Lignin-polysaccharide composite material product and preparation method thereof |
| CN101851428B (en) * | 2010-06-10 | 2012-04-25 | 西安石油大学 | Lignin-glycan composite material product and preparation method thereof |
| CN102677221A (en) * | 2012-06-04 | 2012-09-19 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN102677221B (en) * | 2012-06-04 | 2014-03-26 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN102677222A (en) * | 2012-06-06 | 2012-09-19 | 武汉纺织大学 | Preparation method of high-strength cellulose protein fibers |
| CN102677222B (en) * | 2012-06-06 | 2014-03-26 | 武汉纺织大学 | Preparation method of high-strength cellulose protein fibers |
| CN104004209A (en) * | 2014-06-13 | 2014-08-27 | 东华大学 | Method for preparing polycaprolactone-keratin composite membranes |
| US11840585B2 (en) | 2017-05-05 | 2023-12-12 | Betulium Oy | Cellulose derivatives |
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| CN101168602B (en) | 2010-09-08 |
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