CN102391379A - Preparation method and applications of material used for improving mechanical properties of nitrocellulose - Google Patents
Preparation method and applications of material used for improving mechanical properties of nitrocellulose Download PDFInfo
- Publication number
- CN102391379A CN102391379A CN2011101880077A CN201110188007A CN102391379A CN 102391379 A CN102391379 A CN 102391379A CN 2011101880077 A CN2011101880077 A CN 2011101880077A CN 201110188007 A CN201110188007 A CN 201110188007A CN 102391379 A CN102391379 A CN 102391379A
- Authority
- CN
- China
- Prior art keywords
- nitric acid
- nano
- soluble cotton
- reaction
- filter cake
- 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.)
- Granted
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A preparation method and 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 preparation method and application thereof that improves soluble cotton mechanical property material, belong to macromolecular material preparation and Application Areas.
Background technology
Soluble cotton is that a kind of important containing can industrial chemicals, is widely used in fields such as paint, leather, plastics and fiery explosive.Because soluble cotton belongs to semi-rigid molecular chain, be that the material of base can face all in application process that low temperature becomes fragile, the problem of high temperature deliquescing with it, therefore, improve nitrocellulosic mechanical property is the gordian technique that further promotes its application space comprehensively.
Past people was also attempted adopting interpolation low temperature softening agent, was improved nitrocellulosic mechanical property with methods such as thermoplastic elastomer blending, graft copolymerizations, 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 nitrocellulosic tensile strength, tensile modulus and elongation at break simultaneously in order solving, to propose a kind of preparation method and application thereof that improves soluble cotton mechanical property material.
The objective of the invention is to realize through following technical scheme.
A kind of preparation method who improves soluble cotton mechanical property material, concrete steps are following:
(1) preparation nano-cellulose whisker suspension-s
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.A is centrifugal with reaction solution, removes supernatant liquid, adds water washing, the centrifugal again nano-cellulose whisker suspension-s B that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
Method one: the mixture that in the plain suspension-s B of nanofiber whisker, adds an amount of nitric acid and methylene dichloride; The mass percent of nitric acid is 25%～50% in the mixture, makes the mass percent of nitric acid in reaction system 15%～50% after adding this mixture.In ice bath, react 5min～20min, thin up stops reaction, obtains reaction liquid C.With the reaction liquid C suction filtration, wash to the pH value constant, the nano-cellulose whisker of surperficial nitric acid esterification, its form is a filter cake, is referred to as filter cake D.
Method two: in nano-cellulose suspension-s B, add an amount of nitric acid, make the mass percent of nitric acid in reaction system 15%～50%.React 5min～20min down at 0 ℃～30 ℃, thin up stops reaction, obtains reaction liquid C.With the reaction liquid C suction filtration, wash to the pH value constant, the nano-cellulose whisker of surperficial nitric acid esterification, its form is a filter cake, is referred to as filter cake D.
Method three: in nano-cellulose suspension-s B, add an amount of nitric acid and vitriolic mixture, the mass percent of nitric acid is 12%～50% in the mixture, makes the mass percent of nitric acid in reaction system 10%～30% after adding this mixture.React 5min～20min down at 0 ℃～30 ℃, thin up stops reaction, obtains reaction liquid C.With the reaction liquid C suction filtration, wash to the pH value constant, the nano-cellulose whisker of surperficial nitric acid esterification, its form is a filter cake, is referred to as filter cake D.
Above-mentioned filter cake D is applied among the present invention, in order to solve the problem of improving nitrocellulosic tensile strength, tensile modulus and elongation at break simultaneously.
A kind of application that improves soluble cotton mechanical property material of the present invention, concrete steps are following:
Step 1, the nitric acid esterification of nano-cellulose whisker surface obtain filter cake D;
The dispersion of nano-cellulose whisker in organic solvent of step 2, surperficial nitric acid esterification
Method one: with filter cake D freeze-drying.The nano-cellulose whisker of getting an amount of freeze dried surperficial nitric acid esterification drops in the organic solvent, and ultrasonic oscillation 15min～30min obtains homodisperse suspension-s E in organic solvent.
Method two: the water with among the organic solvent displacement filter cake D obtains homodisperse suspension-s E in organic solvent.
The curtain coating casting of step 3, soluble cotton composite package
Soluble cotton is dissolved among the suspension-s 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 package.
Beneficial effect
(1) the present invention at first provides a kind of surface modifying method of nano-cellulose whisker, can make the nano-cellulose whisker be dispersed in the organic solvent well through this method;
(2) tensile strength of resulting soluble cotton composite package, Young's modulus and three indexs of elongation at break are significantly improved simultaneously.
The practical implementation instance
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-s
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is for use.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.A1 is centrifugal with reaction solution, removes supernatant liquid, adds water washing, the centrifugal again nano-cellulose suspension-s B1 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension-s B1 is added in the mixture of 300g nitric acid and 600g methylene dichloride.In ice bath, react 10min, thin up stops reaction, obtains reaction liquid C 1.With reaction liquid C 1 suction filtration, washing 3 times, get filter cake D1.
(3) dispersion of nano-cellulose whisker in acetone of surperficial nitric acid esterification
With filter cake D1 freeze-drying.The nano-cellulose whisker of freeze dried surperficial nitric acid esterification is dropped in the acetone, and ultrasonic oscillation 30min obtains homodisperse suspension-s E1 in acetone.
Two, the curtain coating of soluble cotton composite package casting
The common soluble cotton of 10g is dissolved in the 100g suspension-s (wherein the mass percent concentration of nano-cellulose is 0.2%), ultrasonic oscillation 3min, curtain coating is cast into the soluble cotton composite package.The test result of soluble cotton composite package mechanical property is seen table 1.
Embodiment 2
One, the nitric acid esterification on nano-cellulose whisker surface
(1) preparation nano-cellulose suspension-s
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is for use.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.A2 is centrifugal with reaction solution, removes supernatant liquid, adds water washing, the centrifugal again nano-cellulose suspension-s B2 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension-s B2 is added in 200g nitric acid and the 700g vitriolic mixture.In 28 ℃, react 5min, 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-s E2 in acetone.
Two, the curtain coating of soluble cotton composite package casting
The common soluble cotton of 10g is dissolved in the 100g suspension-s (wherein the mass percent concentration of nano-cellulose is 0.35%), ultrasonic oscillation 4min, curtain coating is cast into the soluble cotton composite package.The test result of soluble cotton composite package mechanical property is seen table 1.Can see with the soluble cotton blank film and comparing that the tensile strength raising 21.7% of soluble cotton composite package, 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-s
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is for use.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.A3 is centrifugal with reaction solution, removes supernatant liquid, adds water washing, the centrifugal again nano-cellulose suspension-s B3 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension-s B3 is added in the 500g nitric acid.In ice bath, react 5min, 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-s E3 in acetone.
Two, the curtain coating of soluble cotton composite package casting
The common soluble cotton of 10g is dissolved in the 100g suspension-s (wherein the mass percent concentration of nano-cellulose is 0.5%), ultrasonic oscillation 5min, curtain coating is cast into the soluble cotton composite package.The test result of soluble cotton composite package mechanical property is seen table 1.
Embodiment 4
One, the nitric acid esterification on nano-cellulose whisker surface
(1) preparation nano-cellulose suspension-s
11g gossypin powder suction filtration behind the ultrasonic pretreatment 15min, oven dry in ice bath is for use.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.A4 is centrifugal with reaction solution, removes supernatant liquid, adds water washing, the centrifugal again nano-cellulose suspension-s B4 that obtains.
(2) the nitric acid esterification on nano-cellulose whisker surface
100g nano-cellulose suspension-s B4 is added in the mixture of 300g nitric acid and 600g methylene dichloride.In 25 ℃, react 5min, 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-s E4 in the alcohol ether mixing solutions.
Two, the curtain coating of soluble cotton composite package casting
The common soluble cotton of 10g is dissolved in the 100g suspension-s (wherein the mass percent concentration of nano-cellulose is 0.7%), ultrasonic oscillation 3min, curtain coating is cast into the soluble cotton composite package.The test result of soluble cotton composite package mechanical property is seen table 1.
The Mechanics Performance Testing result of table 1 soluble cotton blank film and composite package
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 knowing that tensile strength, Young's modulus and the elongation at break of the soluble cotton composite package that obtains among 4 embodiment of the present invention are apparently higher than the soluble cotton blank film in the table.
Claims (9)
1. a preparation method who improves soluble cotton mechanical property material is characterized in that, may further comprise the steps:
Step 1, preparation nano-cellulose whisker suspension-s
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; A is centrifugal with reaction solution, removes supernatant liquid, adds water washing again, the centrifugal again nano-cellulose whisker suspension-s B that obtains;
The nitric acid esterification on step 2, nano-cellulose whisker surface
Method one: the mixture that in the plain suspension-s B of nanofiber whisker, adds an amount of nitric acid and methylene dichloride; The mass percent of nitric acid is 25%～50% in the mixture, makes the mass percent of nitric acid in reaction system 15%～50% after adding this mixture; In ice bath, react, thin up stops reaction, obtains reaction liquid C; With the reaction liquid C suction filtration, wash to the pH value constant, the nano-cellulose whisker of surperficial nitric acid esterification, its form is a filter cake, is referred to as filter cake D;
Method two: in nano-cellulose suspension-s B, add an amount of nitric acid, make the mass percent of nitric acid in reaction system 15%～50%; 0 ℃～30 ℃ reactions down, thin up stops reaction, obtains reaction liquid C; With the reaction liquid C suction filtration, wash to the pH value constant, the nano-cellulose whisker of surperficial nitric acid esterification, its form is a filter cake, is referred to as filter cake D;
Method three: in nano-cellulose suspension-s B, add an amount of nitric acid and vitriolic mixture, the mass percent of nitric acid is 12%～50% in the mixture, makes the mass percent of nitric acid in reaction system 10%～30% after adding this mixture; 0 ℃～30 ℃ reactions down, thin up stops reaction, obtains reaction liquid C; With the reaction liquid C suction filtration, wash to the pH value constant, the nano-cellulose whisker of surperficial nitric acid esterification, its form is a filter cake, is referred to as filter cake D.
2. a kind of preparation method who 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 preparation method who 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 preparation method who improves soluble cotton mechanical property material as claimed in claim 1 is characterized in that: the reaction times in ice bath described in the step 2 method one is 5min～20min.
5. a kind of preparation method who 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 ℃ following reaction times.
6. a kind of preparation method who 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 ℃ following reaction times.
7. an application that improves soluble cotton mechanical property material is characterized in that, may further comprise the steps: step 1, utilize the described a kind of preparation method who improves soluble cotton mechanical property material of claim one, the filter cake D of system;
The dispersion of nano-cellulose whisker in organic solvent of step 2, surperficial nitric acid esterification
Method one: with filter cake D freeze-drying, get and put in right amount in the organic solvent, ultrasonic oscillation obtains homodisperse suspension-s E in organic solvent;
Method two: the water with in the organic solvent displacement filter cake obtains homodisperse suspension-s E in organic solvent; The curtain coating casting of step 3, soluble cotton composite package
Soluble cotton is dissolved among the suspension-s E, makes 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 package.
8. a kind of application that improves soluble cotton mechanical property material as claimed in claim 6 is characterized in that: the ultrasonic oscillation time described in the step 2 method one is 15min～30min.
9. a kind of application that improves soluble cotton mechanical property material as claimed in claim 6 is characterized in that: the ultrasonic oscillation time described in the step 3 is 0.5min～5min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110188007 CN102391379B (en) | 2011-07-06 | 2011-07-06 | Applications of material used for improving mechanical properties of nitrocellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110188007 CN102391379B (en) | 2011-07-06 | 2011-07-06 | Applications of material used for improving mechanical properties of nitrocellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102391379A true CN102391379A (en) | 2012-03-28 |
| CN102391379B CN102391379B (en) | 2013-04-17 |
Family
ID=45858779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110188007 Active CN102391379B (en) | 2011-07-06 | 2011-07-06 | Applications of material used for improving mechanical properties of nitrocellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102391379B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819710A (en) * | 2014-03-04 | 2014-05-28 | 苏州奥特福环境科技有限公司 | Method for preparing hydrophilic nitrated cellulose film |
| CN107151271A (en) * | 2017-06-05 | 2017-09-12 | 常熟理工学院 | A kind of preparation method of the low quick-fried temperature nitrocotton of high energy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004003184A1 (en) * | 2002-06-30 | 2004-01-08 | Instytut Immunologii I Terapii Doswiadczalnej Pan | A method for obtaining purified bacteriophage preparation s |
| CN101838332A (en) * | 2010-07-09 | 2010-09-22 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
-
2011
- 2011-07-06 CN CN 201110188007 patent/CN102391379B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004003184A1 (en) * | 2002-06-30 | 2004-01-08 | Instytut Immunologii I Terapii Doswiadczalnej Pan | A method for obtaining purified bacteriophage preparation s |
| CN101838332A (en) * | 2010-07-09 | 2010-09-22 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
Non-Patent Citations (1)
| Title |
|---|
| 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》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819710A (en) * | 2014-03-04 | 2014-05-28 | 苏州奥特福环境科技有限公司 | Method for preparing hydrophilic nitrated cellulose film |
| 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 |
| CN107151271A (en) * | 2017-06-05 | 2017-09-12 | 常熟理工学院 | A kind of preparation method of the low quick-fried temperature nitrocotton of high energy |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102391379B (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103044871A (en) | Preparation method of polylactic acid/nano-cellulose composite material | |
| JP2010111707A (en) | Polymer treating agent and dope | |
| CN110396284B (en) | Intumescent flame retardant, flame-retardant polylactic acid material and preparation method thereof | |
| CN109942755B (en) | Synthetic method of cellulose-based ionic liquid self-repairing gel | |
| Li et al. | Structure and properties of regenerated cellulose fibers based on dissolution of cellulose in a CO2 switchable solvent | |
| CN110885476B (en) | Secondary doped graphene oxide/alkali-soluble chitosan-polyaniline-polyacrylamide composite conductive hydrogel prepared by one-pot method | |
| CN105038212A (en) | Oxidized graphene-reinforced nylon material as well as preparation method and application thereof | |
| CN103642190B (en) | Polyethylene glycol modified cyclodextrin, as well as preparation and application thereof | |
| WO2015200589A1 (en) | Production of poly alpha-1,3-glucan films | |
| GB2481824A (en) | Fabrication of cellulose article from dope comprising ionic liquid and aprotic co-solvent | |
| CN103881340A (en) | Preparation method and application for biomass fibre-aliphatic polyester composite material macromolecular coupling agent | |
| CN104788575A (en) | Cellulose derivative containing DOPO structure, and preparation method thereof | |
| CN106930100A (en) | A kind of preparation method of polyimides/graphene oxide complex fiber material | |
| CN102391379B (en) | Applications of material used for improving mechanical properties of nitrocellulose | |
| CN103396570A (en) | Chitin nano-fiber/polyaniline composite film preparation method | |
| CN104479342A (en) | Preparation method of reinforced and toughened thermoplastic polyurethane/regenerated cellulose (TPU/RC) composite film | |
| CN102304238A (en) | Renewable cellulose composite film and preparation method thereof | |
| CN113480800A (en) | Biodegradable plastic and preparation method thereof | |
| CN103834046A (en) | Method for preparing natural cellulose containing zein mixture by using alcoholic solvent | |
| CN106282437A (en) | A kind of based on cellulose and Nano-meter SiO_22the leather retanning agent of hydridization and preparation method | |
| Xie et al. | Preparation of multifunctional chitosan derivative containing 10-undecenoyl and galloyl groups and its application in styrene-butadiene rubber/silica composites | |
| CN101633843A (en) | Preparation method of bromine nitrogen series composite flame retardant | |
| Low et al. | Morphological, thermal, and mechanical properties of natural rubber reinforced with cellulose nanofibers from oil palm empty fruit bunch | |
| JP2014037657A (en) | β-1,3-GLUCAN NANOFIBER AND ITS MANUFACTURING METHOD | |
| CN103819581A (en) | Biodegradable macromolecular carbodiimide and preparation method |
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 |