CN104194060A - Cellulose film and preparation method thereof - Google Patents
Cellulose film and preparation method thereof Download PDFInfo
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- CN104194060A CN104194060A CN201410455397.3A CN201410455397A CN104194060A CN 104194060 A CN104194060 A CN 104194060A CN 201410455397 A CN201410455397 A CN 201410455397A CN 104194060 A CN104194060 A CN 104194060A
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- mierocrystalline cellulose
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Abstract
The invention discloses a cellulose film and a preparation method thereof. The invention aims at providing the cellulose film which has optical transparency, low refractive index, good impact resistance and high cohesiveness, and can be biodegraded, wherein the degradation products are safe and free from pollution. The invention further provides the preparation method of the film. The method is free from any environmental pollution and simple and feasible in process. According to the technical scheme, the cellulose film is formed by hot-pressing a cellulose butyral derivative, belonging to the technical field of films.
Description
Technical field
The invention discloses a kind of film, specifically, is a kind of cellulosefilm, the invention also discloses the preparation method of this cellulosefilm, belongs to thin film technique field.
Background technology
Film is a kind of thin and soft transparent sheet.Make with plastics, tackiness agent, rubber or other materials.Be degradable above owing to placing into the soil 30 days under cellulosefilm normal temperature natural condition.Tradition viscose process is prepared cellulose membrane technique and uses the chemical of the poisonous or severe corrosive such as caustic soda, dithiocarbonic anhydride, sulfuric acid and liquid chlorine, the pollution serious to environment.
It is introduced, Mierocrystalline cellulose is the abundantest natural polymers of nature reserves, and the cellulose amount that annual nature produces exceedes hundred billion tons.As natural, the non-food organism matter of class resource, Mierocrystalline cellulose is considered to the main raw material of human future chemistry, chemical industry.But Mierocrystalline cellulose does not melt, indissoluble solution, what industrial processes Mierocrystalline cellulose adopted is the adhering process of multi-step, complexity.This complex process is tediously long, and condition is difficult to control, and energy consumption is large, and chemical kind used is many, toxicity and corrodibility is strong, consumption is large, and in production process, produces a large amount of poisonous fumes and acidity is large, refractory is managed waste water.Therefore develop cellulosefilm and efficient green new preparation technology has important economy and social effect.
Summary of the invention
For the problems referred to above, last order of the present invention is to provide one, and to have optical transparence, low refractive index, good impact resistance, agglutinating value(of coal) high, the fiber membrane of biodegradable and degraded product safety non-pollution, it is simple that another object of the present invention is to provide a kind of production technique of this film, do not produce any waste gas and waste liquid, be conducive to suitability for industrialized production preparation method.
For solving last technical problem, first technical scheme provided by the invention is such: this cellulosefilm is that the hot pressing of Mierocrystalline cellulose butyral derivative forms.
Above-mentioned cellulosefilm, described derivatived cellulose, its structural unit is as follows:
Wherein: at least one R=
Or
All the other groups are:
Wherein: n is the integer between 300-5000; M is the integer between 1-5.
For preparing this derivatived cellulose, second technical scheme provided by the invention is such: the preparation method of this film is placed on Mierocrystalline cellulose butyral derivative solid between thermocompressor plate, hot pressing at 100～160 DEG C, pressure is 10～30 MPas, after hot pressing 5～20 minutes, at room temperature cooling, form Mierocrystalline cellulose butyral film.
Further, the preparation method of upper film, between described heating platen and Mierocrystalline cellulose butyral derivative solid with ethylene glycol terephthalate divided thin film every.
Compared with prior art, technology tool provided by the invention has the following advantages:
1, the present invention's Mierocrystalline cellulose butyral used is a kind of novel cellulose derivative, can react by Mierocrystalline cellulose the oxygen-(2 that obtains side chain and contain multiple hydroxyls with glycidyl ether, 3-dihydroxypropyl) Mierocrystalline cellulose, then the hydroxyl butyralization on side chain is prepared from.This derivative main chain is cellulosic poly-dextrose residue, and side chain contains ring texture.In Mierocrystalline cellulose butyral macromole, not only contain hydrophilic hydroxyl but also contain hydrophobic butyral group, similar to polyvinyl butyral acetal, there is bond properties.Mierocrystalline cellulose butyral may be dissolved in the organic solvents such as methyl alcohol, pyridine, methyl-sulphoxide and dimethyl formamide, and also melting at a certain temperature, has good film-forming properties, is easily prepared into film.This fibrid element butyral film has good optical transparence, lower refractive index and higher shock resistance, can be used for interlayer film and the photovoltaic component encapsulating material of shatter proof glass.
2, the transparency of the Mierocrystalline cellulose butyral film that prepared by the present invention under visible ray is greater than 80%, refractive index is less than 1.505, elongation at break is between 100～300%, tensile stress is between 1.5～13 MPas, toughness is greater than 2.4 MPas, there is shock resistance, (film soil burial test result at 30 DEG C shows degradable 44% after 9 days, and can degradable one-tenth carbonic acid gas and water after 20 days for biodegradable and degraded product safety non-pollution.), be the high performance environment-friendly material of a class.
3, preparation method provided by the invention adopts hot-formingly, does not use any organic solvent or auxiliary agent, and preparation technology is simple, does not produce any waste gas and waste liquid, is conducive to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose infrared spectrum of the embodiment of the present invention 1;
Fig. 2 is oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose of the embodiment of the present invention 1
13cNMR figure;
Fig. 3 is the Mierocrystalline cellulose butyral derivative of the embodiment of the present invention 1
13c NMR spectrogram;
Fig. 4 is oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose infrared spectrum of the embodiment of the present invention 2;
Fig. 5 is oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose of the embodiment of the present invention 2
13c NMR figure;
Fig. 6 is the Mierocrystalline cellulose butyral derivative of the embodiment of the present invention 2
13c NMR spectrogram;
Fig. 7 is oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose infrared spectrum of the embodiment of the present invention 3;
Fig. 8 is oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose of the embodiment of the present invention 3
13c NMR figure;
Fig. 9 is the Mierocrystalline cellulose butyral derivative of the embodiment of the present invention 3
13cNMR spectrogram;
Embodiment
In order better to understand, implement claim of the present invention, below in conjunction with specific embodiments and the drawings, claim of the present invention is described in further detail, but the present invention is not limited to following embodiment, but is limited with claim.
Embodiment 1
First prepare oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose, its method is as follows:
2g Mierocrystalline cellulose (viscosity-average molecular weight is 120,000) is dispersed in to the mixed aqueous solution that 98g contains 10wt% sodium hydroxide and 8wt% urea and is pre-chilled to-16 DEG C, after 20 hours, thawing to stir obtains transparent cellulose solution.Racemic glycidol is slowly added drop-wise to (time for adding is 24 hours) in cellulose solution, wherein, Racemic glycidol and Mierocrystalline cellulose glucose unit (AGU) mol ratio are 96:1, react 48 hours at 0 DEG C, and adding acetic acid neutralization solution pH value is 6.Obtain oxygen-(2,3-dihydroxypropyl) cellulose prods with 1 week postlyophilization of distill water dialysis again, its substitution value is 1.51, and molar substitution is 6.43, and to this product carry out FT-IR and
13c NMR characterizes, and consults Fig. 1 and Fig. 2.
Prepare Mierocrystalline cellulose butyral derivative, its method is as follows again:
1 gram of oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose (molar substitution is 6.43) is dispersed in 99 grams of distilled water to oxygen-(2,3-dihydroxypropyl) cellulose aqueous solution that preparation concentration is 1wt%.Add 0.5g to make catalyzer to benzene methanesulfonic acid, slowly drip butyraldehyde (mol ratio of butyraldehyde and hydroxyl is 6:1), under 50 DEG C of nitrogen protections, react 24 hours.Reaction solution, after acetone precipitation, is used distill water dialysis one week, obtains Mierocrystalline cellulose butyral derivative after lyophilize, and the molar substitution of butyral group is 0.11, and this product is carried out
13c NMR, consults Fig. 3.
Mierocrystalline cellulose butyral derivative (molar substitution is 0.1) is placed between thermocompressor plate, and between heating platen and Mierocrystalline cellulose butyral derivative solid with ethylene glycol terephthalate divided thin film every, then hot pressing at 100 DEG C, pressure is 30 MPas, and hot pressing is after 20 minutes, at room temperature cooling, the Mierocrystalline cellulose butyral film that formation thickness is 0.4mm, transmittance is 85%, and refractive index is 1.496, and toughness is 5.3 MPas.
Embodiment 2
2g Mierocrystalline cellulose (viscosity-average molecular weight is 50,000) is dispersed in to the mixed aqueous solution that 98g contains 8wt% sodium hydroxide and 8wt% urea and is pre-chilled to-18 DEG C, after 24 hours, thawing to stir obtains transparent cellulose solution.Racemic glycidol is slowly added drop-wise to (time for adding is 5 hours) in cellulose solution, wherein, Racemic glycidol and Mierocrystalline cellulose glucose unit (AGU) mol ratio are 96:1, react 48 hours at 25 DEG C, and adding acetic acid neutralization solution pH value is 6.Obtain oxygen-(2,3-dihydroxypropyl) cellulose prods with 1 week postlyophilization of distill water dialysis again, its substitution value is 1.76, and molar substitution is 9.16, and to this product carry out FT-IR and
13c NMR characterizes, and consults 4 and Fig. 5.
Prepare Mierocrystalline cellulose butyral derivative, its method is as follows again:
2 grams of oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose (molar substitution is 9.16) is dispersed in 98 grams of distilled water to oxygen-(2,3-dihydroxypropyl) cellulose aqueous solution that preparation concentration is 2wt%.Add 2g to make catalyzer to benzene methanesulfonic acid, slowly drip butyraldehyde (mol ratio of butyraldehyde and hydroxyl is 50:1), under 90 DEG C of nitrogen protections, react 20 hours.Reaction solution, after acetone precipitation, is used distill water dialysis one week, obtains Mierocrystalline cellulose butyral derivative after lyophilize, and the molar substitution of butyral group is 3.6.And this product is carried out
13c NMR characterizes, and consults Fig. 6.
Mierocrystalline cellulose butyral derivative (molar substitution is 4.0) is placed between thermocompressor plate, and between heating platen and Mierocrystalline cellulose butyral derivative solid with ethylene glycol terephthalate divided thin film every, then hot pressing at 160 DEG C, pressure is 10 MPas, and hot pressing is after 5 minutes, at room temperature cooling, the Mierocrystalline cellulose butyral film that formation thickness is 0.4mm, transmittance is 80%, and refractive index is 1.501, and toughness is 2.4 MPas.
Embodiment 3
First prepare oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose, its method is as follows:
2g Mierocrystalline cellulose (viscosity-average molecular weight is 90,000) is dispersed in to the mixed aqueous solution that 98g contains 6wt% sodium hydroxide and 10wt% urea and is pre-chilled to-16 DEG C, after 16 hours, thawing to stir obtains transparent cellulose solution.Racemic glycidol is slowly added drop-wise to (time for adding is 24 hours) in cellulose solution, wherein, Racemic glycidol and Mierocrystalline cellulose glucose unit (AGU) mol ratio are 72:1, react 36 hours at 25 DEG C, and adding acetic acid neutralization solution pH value is 7.Obtain oxygen-(2,3-dihydroxypropyl) cellulose prods with 1 week postlyophilization of distill water dialysis again, its substitution value is 1.55, and molar substitution is 8.03, and to this product carry out FT-IR and
13c NMR characterizes, and consults Fig. 7 and Fig. 8.
Prepare Mierocrystalline cellulose butyral derivative, its method is as follows again:
4 grams of oxygen-(2,3-dihydroxypropyl) Mierocrystalline cellulose (molar substitution is 8.03) is dispersed in 96 grams of distilled water to oxygen-(2,3-dihydroxypropyl) cellulose aqueous solution that preparation concentration is 4wt%.Add 1g hydrochloric acid (35wt%) to make catalyzer, slowly drip butyraldehyde (mol ratio of butyraldehyde and hydroxyl is 48:1), under 50 DEG C of nitrogen protections, react 24 hours.Reaction solution, after acetone precipitation, is used distill water dialysis one week, obtains Mierocrystalline cellulose butyral derivative after lyophilize, and the molar substitution of butyral group is 1.16.And this product is carried out
13c NMR characterizes, and consults 9.
Mierocrystalline cellulose butyral derivative (molar substitution is 1.2) is placed between thermocompressor plate, hot pressing at 120 DEG C, pressure is 30 MPas, after hot pressing 8 minutes, the Mierocrystalline cellulose butyral film at room temperature cooling, formation thickness is 0.4mm, transmittance is 86%, refractive index is 1.498, and toughness is 8.7 MPas.
For the advantage of the better explanation film that the present invention provided, provide film that the present invention carries and the film performance parameter comparison table of market sale below.
Claims (4)
1. a cellulosefilm, is characterized in that, described cellulosefilm is that the hot pressing of Mierocrystalline cellulose butyral derivative forms.
2. cellulosefilm according to claim 1, is characterized in that, described Mierocrystalline cellulose butyral derivant structure unit is as follows:
Wherein: at least one R=
Or
All the other groups are:
Wherein: n is the integer between 300-5000; M is the integer between 1-5.
3. the method for preparation film claimed in claim 1, it is characterized in that, the method is that Mierocrystalline cellulose butyral derivative solid claimed in claim 1 is placed between thermocompressor plate, hot pressing at 100～160 DEG C, pressure is 10～30 MPas, after hot pressing 5～20 minutes, at room temperature cooling, form Mierocrystalline cellulose butyral film.
4. the preparation method of film according to claim 3, is characterized in that, between described heating platen and Mierocrystalline cellulose butyral derivative solid with ethylene glycol terephthalate divided thin film every.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096326A (en) * | 1976-10-13 | 1978-06-20 | Hercules Incorporated | Dihydroxypropyl cellulose |
| CN101490091A (en) * | 2006-07-07 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing cellulose acetals |
| CN101835805A (en) * | 2007-10-25 | 2010-09-15 | 花王株式会社 | Method for producing cellulose ether derivative |
| CN103502276A (en) * | 2011-05-02 | 2014-01-08 | 花王株式会社 | Method for producing alkali cellulose |
-
2014
- 2014-09-09 CN CN201410455397.3A patent/CN104194060A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096326A (en) * | 1976-10-13 | 1978-06-20 | Hercules Incorporated | Dihydroxypropyl cellulose |
| CN101490091A (en) * | 2006-07-07 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing cellulose acetals |
| CN101835805A (en) * | 2007-10-25 | 2010-09-15 | 花王株式会社 | Method for producing cellulose ether derivative |
| CN103502276A (en) * | 2011-05-02 | 2014-01-08 | 花王株式会社 | Method for producing alkali cellulose |
Non-Patent Citations (1)
| Title |
|---|
| CHUNYU CHANG，等: "High performance films of cellulose butyral derivative having a necklace-like annular structure in the side chains", 《POLYMER》 * |
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