CN102391379B - Applications of material used for improving mechanical properties of nitrocellulose - Google Patents
Applications of material used for improving mechanical properties of nitrocellulose Download PDFInfo
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Abstract
An applications of a material used for improving the mechanical properties of nitrocellulose belong to the preparation and application fields of the macromolecular material. The preparation method comprises the following specific steps: adding a defined amount of a mixture of nitric acid and dichloromethane, and nitric acid or a mixture of nitric acid and sulfuric acid in nanocellulose whisker suspension, reacting to obtain nanocellulose whiskers of which surface nitric acid is esterified and which is shaped like a filter cake and called a filter cake D; dispersing the filter cake D in an organic solvent, or replacing water of the filter cake D with an organic solvent to obtain the suspension E; and dissolving nitrocellulose in the suspension E to react, and casting to form a film. The three indexes of the obtained nitrocellulose composite film, namely the tensile strength, the elastic modulus and the elongation at break are obviously increased.
Description
Technical field
The present invention relates to a kind of application that improves soluble cotton mechanical property material, belong to Polymer materialspreparation and Application Areas.
Background technology
Soluble cotton is that a kind of important containing can industrial chemicals, is widely used in the fields such as paint, leather, plastics and fiery explosive.Because soluble cotton belongs to semi-rigid molecular chain, low temperature becomes fragile, the problem of high temperature deliquescing for basic material all can face in application process take it, and therefore, improve nitrocellulosic mechanical property is the gordian technique that further promotes its application space comprehensively.
People also attempted adopting interpolation low temperature softening agent, improved nitrocellulosic mechanical property with methods such as thermoplastic elastomer blending, graft copolymerizations in the past, but these methods often can cause other performance index variation in a certain index in improving tensile strength, tensile modulus and elongation at break.
Summary of the invention
To the objective of the invention is the problem of improving simultaneously nitrocellulosic tensile strength, tensile modulus and elongation at break in order solving, to propose a kind of application that improves soluble cotton mechanical property material.
The objective of the invention is to be achieved through the following technical solutions.
A kind of application that improves soluble cotton mechanical property material, concrete steps are as follows:
(1) preparation nano-cellulose whisker suspension
With suction filtration, the oven dry behind ultrasonic pretreatment 5min～20min in ice bath of gossypin powder; Immerse concentration and be in 45%～70% the sulphuric acid soln, liquid-solid ratio is controlled at 17.5～50mL/g; At stirred in water bath reaction 30min～90min of 45 ℃～75 ℃, thin up stops reaction, obtains reaction solution A.Reaction solution A is centrifugal, remove supernatant liquid, add water washing, the more centrifugal nano-cellulose whisker suspension B that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
Method one: the mixture that in nanofiber whisker element suspension B, adds an amount of nitric acid and methylene dichloride, the mass percent of nitric acid is 25%～50% in the mixture, add behind this mixture so that the mass percent of nitric acid in reaction system 15%～50%.React 5min～20min in ice bath, thin up stops reaction, obtains reaction liquid C.With the reaction liquid C suction filtration, to be washed to the pH value constant, gets the nano-cellulose whisker of surperficial nitric acid esterification, its form is filter cake, is referred to as filter cake D.
Method two: in nano-cellulose suspension B, add an amount of nitric acid, make the mass percent of nitric acid in reaction system 15%～50%.At 0 ℃～30 ℃ lower reaction 5min～20min, thin up stops reaction, obtains reaction liquid C.With the reaction liquid C suction filtration, to be washed to the pH value constant, gets the nano-cellulose whisker of surperficial nitric acid esterification, its form is filter cake, is referred to as filter cake D.
Method three: add the mixture of an amount of nitric acid and sulfuric acid in nano-cellulose suspension B, the mass percent of nitric acid is 12%～50% in the mixture, add behind this mixture so that the mass percent of nitric acid in reaction system 10%～30%.At 0 ℃～30 ℃ lower reaction 5min～20min, thin up stops reaction, obtains reaction liquid C.With the reaction liquid C suction filtration, to be washed to the pH value constant, gets the nano-cellulose whisker of surperficial nitric acid esterification, its form is filter cake, is referred to as filter cake D.
(3), the dispersion of nano-cellulose whisker in organic solvent of surperficial nitric acid esterification
Method one: with filter cake D freeze-drying.The nano-cellulose whisker of getting the surperficial nitric acid esterification of an amount of freeze-drying drops in the organic solvent, and ultrasonic oscillation 15min～30min obtains homodisperse suspension E in organic solvent.
Method two: the water with among the organic solvent displacement filter cake D obtains homodisperse suspension E in organic solvent.
(4), the curtain coating of soluble cotton composite membrane casting
Soluble cotton is dissolved among the suspension E, obtains mixing solutions, make the nano-cellulose whisker of surperficial nitric acid esterification account for 2%～15% of soluble cotton quality, ultrasonic oscillation 0.5min～5min, curtain coating is cast into the soluble cotton composite membrane.
Beneficial effect
(1) the present invention at first provides a kind of surface modifying method of nano-cellulose whisker, can be so that the nano-cellulose whisker is dispersed in the organic solvent well by this method;
(2) tensile strength of resulting soluble cotton composite membrane, Young's modulus and three indexs of elongation at break are significantly improved simultaneously.
The implementation example
Below in conjunction with embodiment the present invention is elaborated.
Embodiment 1
One, the nitric acid esterification on nano-cellulose whisker surface
(1) preparation nano-cellulose suspension
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is stand-by.It is that liquid-solid ratio is 17.5mL/g, at 45 ℃ stirred in water bath reaction 45min, adds ten times of water dilutions reaction is stopped, and obtains reaction solution A1 in 64% the sulphuric acid soln that the above-mentioned cellulose powder of 10g is immersed concentration.Reaction solution A1 is centrifugal, remove supernatant liquid, add water washing, the more centrifugal nano-cellulose suspension B1 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension B1 is added in the mixture of 300g nitric acid and 600g methylene dichloride.React 10min in ice bath, thin up stops reaction, obtains reaction liquid C 1.With reaction liquid C 1 suction filtration, washing 3 times, get filter cake) 1.
(3) dispersion of nano-cellulose whisker in acetone of surperficial nitric acid esterification
With filter cake) 1 freeze-drying.The nano-cellulose whisker of the surperficial nitric acid esterification of freeze-drying is dropped in the acetone, and ultrasonic oscillation 30min obtains homodisperse suspension E1 in acetone.
Two, the curtain coating of soluble cotton composite membrane casting
The common soluble cotton of 10g is dissolved in the 100g suspension (wherein the mass percent concentration of nano-cellulose is 0.2%), ultrasonic oscillation 3min, curtain coating is cast into the soluble cotton composite membrane.The test result of soluble cotton composite membrane mechanical property sees Table 1.
Embodiment 2
One, the nitric acid esterification on nano-cellulose whisker surface
(1) preparation nano-cellulose suspension
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is stand-by.It is that liquid-solid ratio is 17.5mL/g, at 45 ℃ stirred in water bath reaction 45min, adds ten times of water dilutions reaction is stopped, and obtains reaction solution A2 in 64% the sulphuric acid soln that the above-mentioned cellulose powder of 10g is immersed concentration.Reaction solution A2 is centrifugal, remove supernatant liquid, add water washing, the more centrifugal nano-cellulose suspension B2 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension B2 is added in the mixture of 200g nitric acid and 700g sulfuric acid.React 5min in 28 ℃, thin up stops reaction, obtains reaction liquid C 2.With reaction liquid C 2 suction filtrations, washing 3 times, get filter cake D2.
(3) dispersion of nano-cellulose whisker in acetone of surperficial nitric acid esterification
With the water among the acetone displacement filter cake D2 3 times, obtain homodisperse suspension E2 in acetone.
Two, the curtain coating of soluble cotton composite membrane casting
The common soluble cotton of 10g is dissolved in the 100g suspension (wherein the mass percent concentration of nano-cellulose is 0.35%), ultrasonic oscillation 4min, curtain coating is cast into the soluble cotton composite membrane.The test result of soluble cotton composite membrane mechanical property sees Table 1.Can see with the soluble cotton blank film and comparing that the tensile strength raising 21.7% of soluble cotton composite membrane, Young's modulus improve 30.3%, elongation at break improves 123.3%.
Embodiment 3
One, the nitric acid esterification on nano-cellulose whisker surface
(1) preparation nano-cellulose suspension
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is stand-by.It is that liquid-solid ratio is 17.5mL/g, at 45 ℃ stirred in water bath reaction 45min, adds ten times of water dilutions reaction is stopped, and obtains reaction solution A3 in 64% the sulphuric acid soln that the above-mentioned cellulose powder of 10g is immersed concentration.Reaction solution A3 is centrifugal, remove supernatant liquid, add water washing, the more centrifugal nano-cellulose suspension B3 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension B3 is added in the 500g nitric acid.React 5min in ice bath, thin up stops reaction, obtains reaction liquid C 3.With reaction liquid C 3 suction filtrations, washing 3 times, get filter cake D3.
(3) dispersion of nano-cellulose whisker in acetone of surperficial nitric acid esterification
With the water among the acetone displacement filter cake D3 3 times, obtain homodisperse suspension E3 in acetone.
Two, the curtain coating of soluble cotton composite membrane casting
The common soluble cotton of 10g is dissolved in the 100g suspension (wherein the mass percent concentration of nano-cellulose is 0.5%), ultrasonic oscillation 5min, curtain coating is cast into the soluble cotton composite membrane.The test result of soluble cotton composite membrane mechanical property sees Table 1.
Embodiment 4
One, the nitric acid esterification on nano-cellulose whisker surface
(1) preparation nano-cellulose suspension
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is stand-by.It is that liquid-solid ratio is 17.5mL/g, at 45 ℃ stirred in water bath reaction 45min, adds ten times of water dilutions reaction is stopped, and obtains reaction solution A4 in 64% the sulphuric acid soln that the above-mentioned cellulose powder of 10g is immersed concentration.Reaction solution A4 is centrifugal, remove supernatant liquid, add water washing, the more centrifugal nano-cellulose suspension B4 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension B4 is added in the mixture of 300g nitric acid and 600g methylene dichloride.React 5min in 25 ℃, thin up stops reaction, obtains reaction liquid C 4.With reaction liquid C 4 suction filtrations, washing 3 times, get filter cake D4.
(3) dispersion of the nano-cellulose whisker of surperficial nitric acid esterification in alcohol-ether mixing solutions (both volume ratios are 1: 1)
With the water among the alcohol ether mixing solutions displacement filter cake D4 3 times, obtain homodisperse suspension E4 in the alcohol ether mixing solutions.
Two, the curtain coating of soluble cotton composite membrane casting
The common soluble cotton of 10g is dissolved in the 100g suspension (wherein the mass percent concentration of nano-cellulose is 0.7%), ultrasonic oscillation 3min, curtain coating is cast into the soluble cotton composite membrane.The test result of soluble cotton composite membrane mechanical property sees Table 1.
The mechanical experimental results of table 1 soluble cotton blank film and composite membrane
The preparation method of soluble cotton blank film is dissolved in the common soluble cotton of 10g in the 100g acetone in the table, ultrasonic concussion 3min, curtain coating casting film.
By the table in as can be known, tensile strength, Young's modulus and the elongation at break of the soluble cotton composite membrane that obtains among 4 embodiment of the present invention are apparently higher than the soluble cotton blank film.
Claims (8)
1. an application that improves soluble cotton mechanical property material is characterized in that, may further comprise the steps: step 1, preparation nano-cellulose whisker suspension
With suction filtration, the oven dry after the ultrasonic pretreatment in ice bath of gossypin powder; Immerse concentration and be in 45%～70% the sulphuric acid soln, liquid-solid ratio is controlled at 17.5～50mL/g; 45 ℃～75 ℃ stirred in water bath reaction, thin up stops reaction, obtains reaction solution A; Reaction solution A is centrifugal, remove supernatant liquid, add again water washing, the more centrifugal nano-cellulose whisker suspension B that obtains;
The nitric acid esterification on step 2, nano-cellulose whisker surface
Method one: the mixture that in nanofiber whisker element suspension B, adds an amount of nitric acid and methylene dichloride, the mass percent of nitric acid is 25%～50% in the mixture, add behind this mixture so that the mass percent of nitric acid in reaction system 15%～50%; React in ice bath, thin up stops reaction, obtains reaction liquid C; With the reaction liquid C suction filtration, to be washed to the pH value constant, gets the nano-cellulose whisker of surperficial nitric acid esterification, its form is filter cake, is referred to as filter cake D;
Method two: in nano-cellulose suspension B, add an amount of nitric acid, make the mass percent of nitric acid in reaction system 15%～50%; 0 ℃～30 ℃ lower reactions, thin up stops reaction, obtains reaction liquid C; With the reaction liquid C suction filtration, to be washed to the pH value constant, gets the nano-cellulose whisker of surperficial nitric acid esterification, its form is filter cake, is referred to as filter cake D;
Method three: add the mixture of an amount of nitric acid and sulfuric acid in nano-cellulose suspension B, the mass percent of nitric acid is 12%～50% in the mixture, add behind this mixture so that the mass percent of nitric acid in reaction system 10%～30%; 0 ℃～30 ℃ lower reactions, thin up stops reaction, obtains reaction liquid C; With the reaction liquid C suction filtration, to be washed to the pH value constant, gets the nano-cellulose whisker of surperficial nitric acid esterification, its form is filter cake, is referred to as filter cake D;
The dispersion of nano-cellulose whisker in organic solvent of step 3, surperficial nitric acid esterification
Method one: with filter cake D freeze-drying; The nano-cellulose whisker of getting the surperficial nitric acid esterification of an amount of freeze-drying drops in the organic solvent, and ultrasonic oscillation obtains homodisperse suspension E in organic solvent;
Method two: the water with among the organic solvent displacement filter cake D obtains homodisperse suspension E in organic solvent;
The curtain coating casting of step 4, soluble cotton composite membrane
Soluble cotton is dissolved among the suspension E, obtains mixing solutions, make the nano-cellulose whisker of surperficial nitric acid esterification account for 2%～15% of soluble cotton quality, ultrasonic oscillation, curtain coating is cast into the soluble cotton composite membrane.
2. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1 is characterized in that: the described ultrasonic pretreatment time of step 1 is 5min～20min.
3. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1 is characterized in that: the described stirred in water bath reaction times at 45 ℃～75 ℃ of step 1 is 30min～90min.
4. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1, it is characterized in that: the reaction times in ice bath described in the step 2 method one is 5min～20min.
5. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1 is characterized in that: described in the step 2 method two is 5min～20min 0 ℃～30 ℃ lower reaction times.
6. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1 is characterized in that: described in the step 2 method three is 5min～20min 0 ℃～30 ℃ lower reaction times.
7. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1, it is characterized in that: the ultrasonic oscillation time described in the step 3 method one is 15min～30min.
8. a kind of application that improves soluble cotton mechanical property material as claimed in claim 1, it is characterized in that: the ultrasonic oscillation time described in the step 4 is 0.5min～5min.
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| CN103819710B (en) * | 2014-03-04 | 2016-02-17 | 苏州奥特福环境科技有限公司 | A kind of preparation method of wetting ability nitrocellulose membrane |
| CN107151271B (en) * | 2017-06-05 | 2019-06-25 | 常熟理工学院 | A kind of preparation method of the low quick-fried temperature nitrocotton of high energy |
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| CN101838332A (en) * | 2010-07-09 | 2010-09-22 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
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| CN101838332A (en) * | 2010-07-09 | 2010-09-22 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
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| 硝化纤维素叠氮甘油醚的制备及表征;邵自强等;《火炸药学报》;20040229;第27卷(第1期);第36-39页 * |
| 邵自强等.硝化纤维素叠氮甘油醚的制备及表征.《火炸药学报》.2004,第27卷(第1期),第36-39页. |
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