CN102660050B - Method for improving mechanical property of cellulose acetate - Google Patents
Method for improving mechanical property of cellulose acetate Download PDFInfo
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- CN102660050B CN102660050B CN201210156736.9A CN201210156736A CN102660050B CN 102660050 B CN102660050 B CN 102660050B CN 201210156736 A CN201210156736 A CN 201210156736A CN 102660050 B CN102660050 B CN 102660050B
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Abstract
The invention relates to a method for improving the mechanical property of cellulose acetate and belongs to the field of preparation and application of high polymer materials. The method comprises the following specific steps of: preparing nano cellulose whisker slurry; uniformly mixing slurry B and glacial acetic acid to obtain slurry C; adding a mixed solution of sulfuric acid, acetic anhydride and the glacial acetic acid into the cooled slurry C to obtain a mixed solution D; stirring the mixed solution D at room temperature, slowly heating to 35 to 55 DEG C, and reacting at the temperature of between 35 and 55 DEG C to obtain reactant E; cooling the reactant E to room temperature, and washing slurry at the bottom by using ethanol and acetone sequentially, and performing suction-filtering to obtain a filter cake F; placing the filter cake F in acetone and performing ultrasonic dispersion to obtain acetic acid esterification nano cellulose suspension G which can suspend stably in acetone; and dissolving cellulose acetate in the suspension G and casting to form a cellulose acetate composite film. According to the method, on the premise of not reducing the light transmittance of the cellulose acetate obviously, the tensile strength, the elastic modulus and the breaking elongation of the cellulose acetate are improved comprehensively.
Description
Technical field
The present invention relates to a kind of method of improving cellulose acetate mechanical property, belong to Polymer materialspreparation and Application Areas.
Background technology
Along with petroleum resources are day by day exhausted, price continues surging, and problem of environmental pollution is outstanding, and biodegradable green material is more and more subject to people's attention and affirms.Mierocrystalline cellulose is the abundantest renewable natural polymer of reserves in the world today, and adopting its derivative to replace traditional synthesizing polymeric material is trend of the times.Cellulose acetate is a kind of important derivatived cellulose, the advantage such as biodegradable owing to having, transmittance is high, easy-formation processing, thermoplasticity are good, is widely used and makes plastics, cigaratte filter, packaging, film, artificial kidney, reverse osmosis membrane, film, liquid crystal material etc.But in its application process, cellulose acetate also exposes the deficiency of the aspect such as mechanical property and thermotolerance.People once attempted with acetyl cellulose blend, it being carried out to modification with polynite, flaxen fiber and nano-titania particle etc., but these methods are often improving in tensile strength, Young's modulus and elongation at break in a certain index, cause other performance index variation, and can cause its transmittance obviously to decline.
Summary of the invention
The object of the invention is, under the prerequisite of not obvious reduction cellulose acetate transmittance, to be not less than under the prerequisite of the initial transmittance 75% of cellulose acetate, improve tensile strength, Young's modulus and the elongation at break of cellulose acetate comprehensively.Thereby a kind of method of improving cellulose acetate mechanical property is proposed.
The object of the invention is to be achieved through the following technical solutions.
A method of improving cellulose acetate mechanical property, concrete steps are as follows:
Step 1: prepare nano-cellulose whisker slurry
It is that in 45%～70% aqueous sulfuric acid, liquid-solid ratio is controlled at 17.5～50mL/g that Mierocrystalline cellulose is immersed to concentration; At the stirred in water bath reaction 15min～90min of 45 DEG C～75 DEG C, thin up stops reaction, obtains reaction solution A.By centrifugal reaction solution A, remove supernatant liquid.Water centrifuge washing 1～2 time, then replace and obtain nano-cellulose whisker slurry B with Glacial acetic acid.
Step 2: the acetic acid esterified on nano-cellulose whisker surface
1) slurry B is evenly mixed with Glacial acetic acid, obtain slurry C; In gained slurry C, the massfraction of nano-cellulose whisker is at 5%-12%;
2) slurry C is cooled to room temperature after swollen 10min～60min at 30 DEG C～60 DEG C;
3) to the mixed solution that adds sulfuric acid, diacetyl oxide and Glacial acetic acid in cooled slurry C, wherein, the quality of sulfuric acid is 1%～10% of nano-cellulose whisker quality, the quality of diacetyl oxide is 0.25-3 times of nano-cellulose whisker quality, the quality of Glacial acetic acid is 5～15 times of nano-cellulose whisker quality, obtains mixed solution D;
5) mixed solution D at room temperature stirs 10min～60min, is then slowly warmed up to 35 DEG C～55 DEG C, and reacts 20min～2h at this temperature, obtains reactant E;
6) by after reactant E cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F.
Step 3: prepare cellulose acetate composite film
1) filter cake F is put into the ultrasonic dispersion of acetone, obtain the acetic acid esterified nano-cellulose suspension G of stable suspersion in acetone;
2) cellulose acetate is dissolved in the suspension G of step 1 gained, wherein, the nano-cellulose of acetic acid esterified accounts for 1%～20% of cellulose acetate quality.Ultrasonic concussion; Curtain coating is cast into cellulose acetate composite film.
Beneficial effect
(1) a kind of method of improving cellulose acetate mechanical property of the present invention, by this method can make nano-cellulose whisker well suspended dispersed in acetone, alcohol-ether mixture equal solvent;
(2) a kind of method of improving cellulose acetate mechanical property of the present invention, because the size of nano-cellulose is less than visible wavelength, visible ray can directly pass through matrix material, and the nano-cellulose of acetic acid esterified can be dispersed in cellulose acetate, therefore, the transmittance of prepared cellulose acetate composite film is more than 70%;
(3) the present invention be with degradable nano-cellulose whisker be filler, because the intensity of nano-cellulose whisker is high, Young's modulus is high, in addition the dimensional effect of nano-cellulose whisker uniqueness, surface and interface effect improved tensile strength, Young's modulus and the elongation at break of cellulose acetate diaphragm simultaneously.
(4) a kind of method of improving cellulose acetate mechanical property of the present invention, the prepared filter cake F of step 2 disperses through ultrasonic wave in acetone, alcohol-ether mixture equal solvent, can obtain stable suspension.
Brief description of the drawings
Fig. 1 is transmittance and the wavelength relationship curve of the acetic acid esterified modifying nanometer cellulose cellulose acetate composite film that obtains of the present invention.
Concrete embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1
One, the surperficial acetic acid esterified of nano-cellulose whisker
(1) prepare nano-cellulose whisker slurry
20g Mierocrystalline cellulose is immersed in the sulphuric acid soln that concentration is 64%, and liquid-solid ratio is 17.5mL/g, and at the stirred in water bath reaction 20min of 45 DEG C, thin up stops reaction, obtains reaction solution A1.By centrifugal reaction solution A1, remove supernatant liquid.Water centrifuge washing 2 times, then replace and obtain nano-cellulose whisker slurry B1 with Glacial acetic acid.
(2) acetic acid esterified on nano-cellulose whisker surface
1) 4g slurry B1 is mixed with 10g Glacial acetic acid, obtain slurry C1;
2) make slurry C1 after swollen 15min, be cooled to room temperature at 40 DEG C;
3) toward the mixed solution that adds 0.01g sulfuric acid, 0.2g diacetyl oxide and 3g Glacial acetic acid in cooled slurry C1, obtain mixed solution D1;
5) mixed solution D1 at room temperature stirs 20min, is then slowly warmed up to 40 DEG C, and keeps 40min at this temperature, obtains reactant E1;
6) by after reactant E1 cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F1.
Two, prepare cellulose acetate composite film
1) undried filter cake F1 (containing 0.12g nano-cellulose whisker) is put into the ultrasonic dispersion of 60g acetone, obtain the acetic acid esterified nano-cellulose suspension G1 of stable suspersion in acetone;
2) 5.88g cellulose acetate is dissolved in suspension G1, ultrasonic oscillation 2h, curtain coating is cast into cellulose acetate composite film, the quality of acetic acid esterified nano-cellulose accounts for 2% of composite membrane quality, the test result of cellulose acetate composite film mechanical property is as shown in table 1, tensile strength is 42.7MPa, and Young's modulus is 1282.7MPa, and elongation at break is 15.6%.The transmittance of cellulose acetate composite film as shown in Figure 1, is 84.3% at the transmittance at 550nm place.
Embodiment 2
One, the surperficial acetic acid esterified of nano-cellulose whisker
(1) prepare nano-cellulose whisker slurry
20g Mierocrystalline cellulose is immersed in the sulphuric acid soln that concentration is 64%, and liquid-solid ratio is 17.5mL/g, and at the stirred in water bath reaction 20min of 45 DEG C, thin up stops reaction, obtains reaction solution A2.By centrifugal reaction solution A2, remove supernatant liquid.Water centrifuge washing 2 times, then replace and obtain nano-cellulose whisker slurry B2 with Glacial acetic acid.
(2) acetic acid esterified on nano-cellulose whisker surface
1) 4g slurry B2 is mixed with 15g Glacial acetic acid, obtain slurry C2;
2) make slurry C2 after swollen 25min, be cooled to room temperature at 35 DEG C;
3) toward the mixed solution that adds 0.005g sulfuric acid, 0.15g diacetyl oxide and 4g Glacial acetic acid in cooled slurry C2, obtain mixed solution, obtain mixed solution D2;
5) mixed solution D2 at room temperature stirs 15min, is then slowly warmed up to 50 DEG C, and keeps 1.5h at this temperature, obtains reactant E2;
6) by after reactant E2 cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F2.
Two, prepare cellulose acetate composite film
1) undried filter cake F2 (containing 0.18g nano-cellulose whisker) is put into the ultrasonic dispersion of 60g acetone, obtain the acetic ester nano-cellulose suspension G2 of stable suspersion in acetone;
2) 5.82g cellulose acetate is dissolved in suspension G2, ultrasonic oscillation 2h, curtain coating is cast into cellulose acetate composite film, the quality of acetic acid esterified nano-cellulose accounts for 3% of composite membrane quality, the test result of cellulose acetate composite film mechanical property is as shown in table 1, tensile strength is 42.2MPa, and Young's modulus is 1328.6MPa, and elongation at break is 18.1%.The transmittance of cellulose acetate composite film as shown in Figure 1, is 82.0% at the transmittance at 550nm place.
Embodiment 3
One, the surperficial acetic acid esterified of nano-cellulose whisker
(1) prepare nano-cellulose whisker slurry
20g Mierocrystalline cellulose is immersed in the sulphuric acid soln that concentration is 64%, and liquid-solid ratio is 17.5mL/g, and at the stirred in water bath reaction 20min of 45 DEG C, thin up stops reaction, obtains reaction solution A3.By centrifugal reaction solution A3, remove supernatant liquid.Water centrifuge washing 2 times, then replace and obtain nano-cellulose whisker slurry B3 with Glacial acetic acid.
(2) acetic acid esterified on nano-cellulose whisker surface
1) 4g slurry B3 is mixed with 13g Glacial acetic acid, obtain slurry C3;
2) make slurry C3 after swollen 20min, be cooled to room temperature at 50 DEG C;
3) toward the mixed solution that adds 0.008g sulfuric acid, 0.6g diacetyl oxide and 5g Glacial acetic acid in cooled slurry C3, obtain mixed solution D3;
5) mixed solution D3 at room temperature stirs 15min, is then slowly warmed up to 50 DEG C, and keeps 1h at this temperature, obtains reactant E3;
6) by after reactant E3 cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F3.
Two, prepare cellulose acetate composite film
1) undried filter cake F3 (containing 0.21g nano-cellulose whisker) is put into the ultrasonic dispersion of 60g acetone, obtain the acetic acid esterified nano-cellulose suspension G3 of stable suspersion in acetone;
2) 5.79g cellulose acetate is dissolved in suspension G3, ultrasonic oscillation 2h, curtain coating is cast into cellulose acetate composite film, the quality of acetic acid esterified nano-cellulose accounts for 3.5% of composite membrane quality, the test result of cellulose acetate composite film mechanical property is as shown in table 1, tensile strength is 43.9MPa, and Young's modulus is 1431.5MPa, and elongation at break is 20.4%.The transmittance of cellulose acetate composite film as shown in Figure 1, is 78.3% at the transmittance at 550nm place.
Embodiment 4
One, the surperficial acetic acid esterified of nano-cellulose whisker
(1) prepare nano-cellulose whisker slurry
20g Mierocrystalline cellulose is immersed in the sulphuric acid soln that concentration is 64%, and liquid-solid ratio is 17.5mL/g, and at the stirred in water bath reaction 20min of 45 DEG C, thin up stops reaction, obtains reaction solution A4.By centrifugal reaction solution A4, remove supernatant liquid.Water centrifuge washing 2 times, then replace and obtain nano-cellulose whisker slurry B4 with Glacial acetic acid.
(2) acetic acid esterified on nano-cellulose whisker surface
1) 4g slurry B4 is mixed with 8g Glacial acetic acid, obtain slurry C4;
2) make slurry C4 after swollen 30min, be cooled to room temperature at 45 DEG C;
3) toward the mixed solution that adds 0.02g sulfuric acid, 0.4g diacetyl oxide and 2g Glacial acetic acid in cooled slurry C4, obtain mixed solution D4;
5) mixed solution D4 at room temperature stirs 10min, is then slowly warmed up to 45 DEG C, and keeps 30min at this temperature, obtains reactant E4;
6) by after reactant E4 cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F4.
Two, prepare cellulose acetate composite film
1) undried filter cake F4 (containing 0.27g nano-cellulose whisker) is put into the ultrasonic dispersion of 60g acetone, obtain the acetic acid esterified nano-cellulose suspension G4 of stable suspersion in acetone;
2) 5.73g cellulose acetate is dissolved in suspension G4, ultrasonic oscillation 2h, curtain coating is cast into cellulose acetate composite film, the quality of acetic acid esterified nano-cellulose accounts for 4.5% of composite membrane quality, the test result of cellulose acetate composite film mechanical property is as shown in table 1, tensile strength is 44.2MPa, and Young's modulus is 1509.0MPa, and elongation at break is 19.4%.The transmittance of cellulose acetate composite film as shown in Figure 1, is 76.2% at the transmittance at 550nm place.
Embodiment 5
One, the surperficial acetic acid esterified of nano-cellulose whisker
(1) prepare nano-cellulose whisker slurry
20g Mierocrystalline cellulose is immersed in the sulphuric acid soln that concentration is 64%, and liquid-solid ratio is 17.5mL/g, and at the stirred in water bath reaction 20min of 45 DEG C, thin up stops reaction, obtains reaction solution A5.By centrifugal reaction solution A5, remove supernatant liquid.Water centrifuge washing 2 times, then replace and obtain nano-cellulose whisker slurry B5 with Glacial acetic acid.
(2) acetic acid esterified on nano-cellulose whisker surface
1) 4g slurry B5 is mixed with 12g Glacial acetic acid, obtain slurry C5;
2) make slurry C5 after swollen 60min, be cooled to room temperature at 55 DEG C;
3) toward the mixed solution that adds 0.025g sulfuric acid, 1g diacetyl oxide and 3.5g Glacial acetic acid in cooled slurry C5, obtain mixed solution D5;
5) mixed solution D5 at room temperature stirs 15min, is then slowly warmed up to 55 DEG C, and keeps 20min at this temperature, obtains reactant E5;
6) by after reactant E5 cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F5.
Two, prepare cellulose acetate composite film
1) undried filter cake F5 (containing 0.42g nano-cellulose whisker) is put into the ultrasonic dispersion of 60g acetone, obtain the acetic acid esterified nano-cellulose suspension G5 of stable suspersion in acetone;
2) 5.58g cellulose acetate is dissolved in suspension G5, ultrasonic oscillation 2h, curtain coating is cast into cellulose acetate composite film, the quality of acetic acid esterified nano-cellulose accounts for 7% of composite membrane quality, the test result of cellulose acetate composite film mechanical property is as shown in table 1, tensile strength is 40.9MPa, and Young's modulus is 1250.6MPa, and elongation at break is 15.0%.The transmittance of cellulose acetate composite film as shown in Figure 1, is 70.1% at the transmittance at 550nm place.
The tensile mechanical properties of table 1 cellulose acetate blank film and composite membrane
In table 1, the preparation method of cellulose acetate blank film is dissolved in 6g cellulose acetate in 60g acetone, ultrasonic oscillation 2h after dissolving completely, and curtain coating is cast into cellulose acetate membrane.
From in table 1, tensile strength, Young's modulus and the elongation at break of the cellulose acetate composite film obtaining in 5 embodiment of the present invention are all higher than cellulose acetate blank film.In composite membrane, tensile strength is up to 44.2MPa, has improved 9% compared with blank film; Young's modulus is up to 1509.0MPa, has improved 39% compared with blank film; Elongation at break is up to 20.4%, has improved 51% compared with blank film.
As shown in Figure 1, added after the nano-cellulose of acetic acid esterified, cellulose acetate diaphragm has all kept higher transmittance.Even added in embodiment 5 after the nano-cellulose of 7% acetic acid esterified, cellulose acetate membrane also reaches 70.1% to the transmittance of 550nm ripple, is 77.5% of blank film.
Above-described specific descriptions; object, technical scheme and beneficial effect to invention further describe; institute is understood that; the foregoing is only specific embodiments of the invention; the protection domain being not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (3)
1. a method of improving the mechanical property of cellulose acetate membrane, is characterized in that: concrete steps are as follows:
Step 1: prepare nano-cellulose whisker slurry
It is that in 45%～70% aqueous sulfuric acid, liquid-solid ratio is controlled at 17.5～50mL/g that Mierocrystalline cellulose is immersed to concentration; The stirred in water bath reaction of 45 DEG C～75 DEG C, thin up stops reaction, obtains reaction solution A; By centrifugal reaction solution A, remove supernatant liquid; Water centrifuge washing 1～2 time, then replace and obtain nano-cellulose whisker slurry B with Glacial acetic acid;
Step 2: the acetic acid esterified on nano-cellulose whisker surface
1) slurry B is evenly mixed with Glacial acetic acid, obtain slurry C; In gained slurry C, the massfraction of nano-cellulose whisker is at 5%-12%;
2) slurry C is cooled to room temperature after swollen at 30 DEG C～60 DEG C;
3) to the mixed solution that adds sulfuric acid, diacetyl oxide and Glacial acetic acid in cooled slurry C, wherein, the quality of sulfuric acid is 1%～10% of nano-cellulose whisker quality, diacetyl oxide quality is 0.25 times of nano-cellulose whisker quality, Glacial acetic acid quality is 5～15 times of nano-cellulose whisker quality, obtains mixed solution D;
4) mixed solution D at room temperature stirs 10min～60min, is then slowly warmed up to 35 DEG C～55 DEG C, and reacts 20min～2h at this temperature, obtains reactant E;
5) by after reactant E cool to room temperature, centrifugal, remove supernatant liquor, the slurry of bottom is successively with ethanol and washing with acetone, and suction filtration obtains the nano-cellulose whisker of acetic acid esterified, is called filter cake F;
Step 3: prepare cellulose acetate composite film
1) filter cake F is put into the ultrasonic dispersion of acetone, obtain the acetic acid esterified nano-cellulose suspension G of stable suspersion in acetone;
2) cellulose acetate is dissolved in to step 3 1) in the suspension G of gained; Ultrasonic concussion; Curtain coating is cast into cellulose acetate composite film; Wherein, the nano-cellulose of acetic acid esterified accounts for 2%～4.5% of cellulose acetate composite film quality.
2. the method for a kind of mechanical property of improving cellulose acetate membrane as claimed in claim 1, is characterized in that: the stirring reaction time in described step 1 is 15min～90min; Described step 2 2) in the swollen time be 10min～60min.
3. the method for a kind of mechanical property of improving cellulose acetate membrane as claimed in claim 1, is characterized in that: the transmittance of the cellulose acetate composite film that described step 3 makes is not less than 75% of the initial transmittance of cellulose acetate.
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| CN103382225B (en) * | 2013-07-22 | 2015-12-02 | 浙江理工大学 | A kind of method of modifying of Cellulose nanocrystal surface esterification |
| CN103467920B (en) * | 2013-09-12 | 2015-05-06 | 北京理工大学 | Method for improving mechanical property and heat resistance property of epoxy resin |
| CN104532378B (en) * | 2014-12-16 | 2017-02-22 | 广东中烟工业有限责任公司 | Method for improving spinnability of acetate fibers |
| CN108290962B (en) * | 2015-09-17 | 2022-03-29 | 美罗迪亚有限公司 | NCC film and products based on NCC film |
| US11905342B2 (en) * | 2015-09-17 | 2024-02-20 | Melodea Ltd. | NCC films and products based thereon |
| CN108440929A (en) * | 2018-05-14 | 2018-08-24 | 周元 | A kind of novel environment friendly nanocomposite and preparation method thereof |
| JP7323887B2 (en) | 2019-02-28 | 2023-08-09 | 国立大学法人北海道大学 | cellulose acetate film |
| CN111992057A (en) * | 2020-07-30 | 2020-11-27 | 江苏天佑新材料科技有限公司 | Preparation method of modified regenerated cellulose hollow dialysis membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200128A (en) * | 1995-09-29 | 1998-11-25 | 罗狄亚化学公司 | Surface-modified cellulose microfibrils method for making same, and use thereof as a filler in composite materials |
| US20080108772A1 (en) * | 2006-11-08 | 2008-05-08 | Ntnu Technology Transfer As | Nanocomposites based on cellulose whiskers and cellulose plastics |
| CN101838332A (en) * | 2010-07-09 | 2010-09-22 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
| WO2011108461A1 (en) * | 2010-03-05 | 2011-09-09 | オリンパス株式会社 | Cellulose nanofibers, method for producing same, composite resin composition and molded body |
-
2012
- 2012-05-18 CN CN201210156736.9A patent/CN102660050B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200128A (en) * | 1995-09-29 | 1998-11-25 | 罗狄亚化学公司 | Surface-modified cellulose microfibrils method for making same, and use thereof as a filler in composite materials |
| US20080108772A1 (en) * | 2006-11-08 | 2008-05-08 | Ntnu Technology Transfer As | Nanocomposites based on cellulose whiskers and cellulose plastics |
| WO2011108461A1 (en) * | 2010-03-05 | 2011-09-09 | オリンパス株式会社 | Cellulose nanofibers, method for producing same, composite resin composition and molded body |
| CN101838332A (en) * | 2010-07-09 | 2010-09-22 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
Non-Patent Citations (4)
| Title |
|---|
| 于忠玺等.纤维素的酸处理及醋酸酯化表面改性研究.《化学与生物工程》.2009,第26卷(第7期),第83-88页. * |
| 王能等.纳米微晶纤维素表面改性研究.《高分子学报》.2006,(第8期),第982-987页. * |
| 纤维素的酸处理及醋酸酯化表面改性研究;于忠玺等;《化学与生物工程》;20090725;第26卷(第7期);第83-88页 * |
| 纳米微晶纤维素表面改性研究;王能等;《高分子学报》;20060830(第8期);第982-987页 * |
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