CN104004101A - Preparation method for acetylated nanocellulose crystal - Google Patents
Preparation method for acetylated nanocellulose crystal Download PDFInfo
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- CN104004101A CN104004101A CN201310061123.1A CN201310061123A CN104004101A CN 104004101 A CN104004101 A CN 104004101A CN 201310061123 A CN201310061123 A CN 201310061123A CN 104004101 A CN104004101 A CN 104004101A
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- acetylize
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Abstract
The invention relates to a preparation method for an acetylated nanocellulose crystal. The method adopts an anhydrous phosphoric acid system to disperse a cellulose raw material, and can perform acetylation directly without separation, thus preparing the acetylated nanocellulose crystal with a cellulose II structure by a one-pot process. The anhydrous phosphoric acid system not only serves as dispersant of the cellulose raw material, but also play a catalyst role in the acetylation process.
Description
Technical field
The present invention relates to a kind of preparation method of modified nanometer cellulose crystal, particularly one of acetylize nano cellulose crystal pot of preparation method.
Background technology
Mierocrystalline cellulose comprises crystallizing field and pars amorpha.These crystal and unbodied Mierocrystalline cellulose rely in its molecule and maintain macromolecular structure and fibriilar form with intermolecular hydrogen bond and Van der Waals force.The performance that nano cellulose crystal is renewable, multiple excellence is enriched, had in source, bar-shaped or thread nanofiber have very high intensity and physical properties, can be used as the reinforcement of multiple matrix material.But, nano cellulose crystal rich surface hydroxyl, poor with non-polar solvent or substrate material consistency, be difficult to disperse.This point makes the application of nano cellulose crystal be defined in the aqueous solution or polar material.In order to overcome this problem, there is a lot of research about nano cellulose crystal surface modification.These method of modifying comprise non covalent bond surface modification, oxidation, acetylize, silanization, sulfonation, carboxylated, cationization and graft copolymerization etc., and in these methods, acetylize is one of method of modifying of tool application prospect.
Have much about the preparation method of acetylize nano cellulose crystal, but all need multiple steps to complete.At present, no matter be that acid-hydrolysis method or ultrasonic method are prepared nano cellulose crystal, be substantially all to carry out in the middle of water, acquisition be the aqeous suspension of nano-cellulose.These water need to be removed, because acetylize requirement must be anhydrous condition.But, the removal process of the aqeous suspension of nano-cellulose bothers very much, and simple being dried can make nano-cellulose again reunite, be difficult to redispersion, and solvent exchange need to consume a large amount of solvents and time, lyophilize, except very consuming time, also needs to consume more energy.Therefore, adopt one kettle way to prepare acetylize nano cellulose crystal, i.e. economy environmental protection again.There is research to adopt expensive ionic liquid to carry out solvent cellulosic material, then carry out acetylize, obtained acetylize nano-cellulose, but cellulose crystals structure deteriorate is serious, can not prepare acetylize nano cellulose crystal.
Summary of the invention
Object of the present invention aims to provide a kind of preparation method of acetylize nano cellulose crystal.Nano-cellulose rich surface is strong containing free hydroxyl group, polarity, is difficult to disperse, consistency is poor, is broadened application scope in organic solvent and low-pole material, and effects on surface hydroxyl carries out acetylize, preparation acetylize nano cellulose crystal.Mostly method is in the past first to separate prepares nano-cellulose aqeous suspension, carries out acetylize after dewatering again, and the process wherein dewatering trouble and consumption are large.For this shortcoming, the present invention adopts anhydrous phosphoric acid system to disperse cellulosic material, directly carries out acetylize without separating, and one kettle way has been prepared acetylize nano cellulose crystal.Anhydrous phosphoric acid system is not only the dispersion agent of cellulosic material, has also played the effect of catalyzer in acetylizad process.
The present invention includes following steps: one, Mierocrystalline cellulose disperses: adopt anhydrous phosphoric acid system to be dispersed into collosol state the cellulosic materials such as cotton fibre.Two, acetylize: add diacetyl oxide generation acetylization reaction in step 1 product.Three, the separation of acetylize nano cellulose crystal: step 2 product, with frozen water dilution or with the neutralization of ice alkali lye, is then carried out to centrifugation, freezing or spraying is dried, and can obtain acetylize nano cellulose crystal.This preparation method is one kettle way preparation, and intermediate product is without separation.
Raw material described in step 1 is the cellulosic materials such as cotton fibre, comprises in addition Microcrystalline Cellulose etc.The solvent system adopting is the anhydrous phosphoric acid system being mixed by polyphosphoric acid and 75%～85% phosphoric acid solution, P
2o
5content is 70%～85%.The mass ratio of cellulosic material and anhydrous phosphoric acid system is 0.04～0.80:1.Dispersion condition is: at temperature-20 DEG C～65 DEG C of temperature, stir 10min～200min.
The mass ratio of the add-on of diacetyl oxide described in step 2 and cellulosic material is 0.3～3.0:1.Temperature of reaction is 0 DEG C～60 DEG C, and the reaction times is 10min～24h.Acetylation reagent is not limited to diacetyl oxide, can also be Acetyl Chloride 98Min., acetyl bromide, acetic acid etc.Reaction is preferably acetylize; but be not limited to acetylize; can also be propionyl, Butyrylation, maleylation, bay acidylate, grease acidylate etc.; obtaining corresponding product is the nano cellulose crystal of propionyl, Butyrylation, maleylation, bay acidylate, grease acidylate, be respectively corresponding acid anhydrides, carboxylic acid halides or acid to the acylating reagent being applied to.The acetylize nano cellulose crystal of preparation belongs to cellulose Ⅱ type structure, and crystal diameter is about 3nm～10nm, and length is about 30nm～500nm, and length-to-diameter ratio is about 10-50.
Compared with prior art, its remarkable advantage of the present invention is:
1. this preparation method is one kettle way preparation, and intermediate product, without separation, can reduce costs greatly.
2. adopting anhydrous phosphoric acid system is dispersion agent, and cost is low, little to cellulose crystals structural damage degree, in cellulosic acetylize, can also play katalysis.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of gossypin raw material (A), product acetylize nano cellulose crystal (B), and Fig. 2 is the solid-state nuclear magnetic resonance spectrogram of product acetylize nano cellulose crystal, has illustrated that Mierocrystalline cellulose is by successful acetylize.Fig. 3 is the transmission electron microscope picture of product acetylize nano cellulose crystal, and Fig. 4 is the field emission scanning electron microscope figure of product acetylize nano cellulose crystal, has determined the nanocrystal state of product.Fig. 5 is the X-ray diffraction spectrogram of product acetylize nano cellulose crystal, illustrates that product crystalline structure is cellulose Ⅱ type.
Embodiment
Embodiment one: 4g absorbent cotton is added to 56g P
2o
5content is, in 75% anhydrous phosphoric acid system, constantly to stir, to colloidal sol shape at 55 DEG C with glass stick.In colloidal sol body, add 50g diacetyl oxide, stirring reaction 3h at 40 DEG C.Reaction product is poured in frozen water, obtained white emulsion.This white emulsion is first separated to 5min under the rotating speed of 2000r/min, discard lower sediment, then separate 10min under rotating speed with 8000r/min, discard supernatant liquid, then add deionized water dilution, more centrifugal, several repeatedly.Spray-dried again, obtain acetylize nano cellulose crystal.
Embodiment two: by 4g Microcrystalline Cellulose and 5g P
2o
5content is 70% anhydrous phosphoric acid system kneading, and constantly stirs with glass stick at 35 DEG C, to colloidal sol shape.In colloidal sol body, add 3g diacetyl oxide, stirring reaction 12h at 20 DEG C.Other are identical with embodiment one.
Embodiment three: by 4g cotton and 20g P
2o
5content is 85% anhydrous phosphoric acid system kneading, and constantly stirs with glass stick at 20 DEG C, to colloidal sol shape.In colloidal sol body, add 1.2g Acetyl Chloride 98Min., stirring reaction 10min at 50 DEG C.Other are identical with embodiment one.
Embodiment four: by 4g alpha-cellulose and 10g P
2o
5content is 73% anhydrous phosphoric acid system kneading, and constantly stirs with glass stick at 60 DEG C, to colloidal sol shape.In colloidal sol body, add 100g diacetyl oxide, stirring reaction 24h at 20 DEG C.Other are identical with embodiment one.
Embodiment five: by 4g cellulose powder and 96g P
2o
5content is 72% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 35 DEG C, to colloidal sol shape.In colloidal sol body, add 20g butyryl oxide, stirring reaction 6h at 20 DEG C.Other are identical with embodiment one.
Embodiment six: by 4g alpha-cellulose and 28g P
2o
5content is 84% anhydrous phosphoric acid system kneading, and constantly stirs with glass stick at-20 DEG C, to colloidal sol shape.In colloidal sol body, add 1.5g propionyl bromide, stirring reaction 0.5h at 0 DEG C.Other are identical with embodiment one.
Embodiment seven: by 4g needle pulpboard and 36g P
2o
5content is 79% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 55 DEG C, to colloidal sol shape.In colloidal sol body, add 75g diacetyl oxide, stirring reaction 24h at 10 DEG C.Other are identical with embodiment one.
Embodiment eight: by 4g flax fiber element and 46g P
2o
5content is 80% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 40 DEG C, to colloidal sol shape.In colloidal sol body, add 25g propionic anhydride, stirring reaction 12h at 40 DEG C.Other are identical with embodiment one.
Embodiment nine: by 4g grass fiber element and 56g P
2o
5content is 76% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 35 DEG C, to colloidal sol shape.In colloidal sol body, add 20g maleic anhydride, stirring reaction 18h at 50 DEG C.Other are identical with embodiment one.
Embodiment ten: by 4g linters and 66g P
2o
5content is 71% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 40g maleic anhydride, stirring reaction 18h at 60 DEG C.Other are identical with embodiment one.
Embodiment 11: by 4g Microcrystalline Cellulose and 76g P
2o
5content is 74% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 60g oxalyl chloride, stirring reaction 1h at 50 DEG C.Other are identical with embodiment one.
Embodiment 12: by 4g Microcrystalline Cellulose and 86g P
2o
5content is 75% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 80g Benzoyl chloride, stirring reaction 2h at 40 DEG C.Other are identical with embodiment one.
Embodiment 13: by 4g absorbent cotton and 96g P
2o
5content is 81% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 100g stearic acid, stirring reaction 24h at 60 DEG C.Other are identical with embodiment one.
Embodiment 14: by 4g cotton and 92g P
2o
5content is 77% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 120g stearic anhydride, stirring reaction 18h at 40 DEG C.Other are identical with embodiment one.
Embodiment 15: by 4g Microcrystalline Cellulose and 81g P
2o
5content is 83% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 100g oleic acid acyl chlorides, stirring reaction 10h at 30 DEG C.Other are identical with embodiment one.
Embodiment 16: by 4g needle pulpboard and 71g P
2o
5content is 78% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 80g lauric acid, stirring reaction 18h at 60 DEG C.Other are identical with embodiment one.
Embodiment 17: by 4g alpha-cellulose and 60g P
2o
5content is 82% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 60g lauric anhydride, stirring reaction 10h at 50 DEG C.Other are identical with embodiment one.
Embodiment 18: by 4g linters and 52g P
2o
5content is 74% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 50g oil anhydride, stirring reaction 24h at 30 DEG C.Other are identical with embodiment one.
Embodiment 19: by 4g cellulose powder and 36g P
2o
5content is 76% anhydrous phosphoric acid system mixing, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 40g oleic acid, stirring reaction 18h at 50 DEG C.Other are identical with embodiment one.
Embodiment 20: by 4g Microcrystalline Cellulose and 16g P
2o
5content is 75% anhydrous phosphoric acid system kneading, and constantly stirs with glass stick at 25 DEG C, to colloidal sol shape.In colloidal sol body, add 20g lauroyl chloride, stirring reaction 10h at 30 DEG C.Other are identical with embodiment one.
Claims (11)
1. a preparation method for acetylize nano cellulose crystal, is characterized in that the preparation process of acetylize nano cellulose crystal is as follows: one, Mierocrystalline cellulose disperses: adopt anhydrous phosphoric acid system to be dispersed into collosol state the cellulosic materials such as Microcrystalline Cellulose.Two, acetylize: add diacetyl oxide generation acetylization reaction in step 1 product.Three, the separation of acetylize nano cellulose crystal, dry: step 2 product, with frozen water dilution or with the neutralization of ice alkali lye, is carried out to freezing or spraying and is dried after centrifugation, obtain acetylize nano cellulose crystal.
2. the preparation method of acetylize nano cellulose crystal according to claim 1, is characterized in that this preparation method is one kettle way preparation, and intermediate product is without separation.
3. the preparation method of acetylize nano cellulose crystal according to claim 1; it is characterized in that the raw material described in step 1 is the cellulosic materials such as Microcrystalline Cellulose, comprises absorbent cotton, cotton, linters, cellulose powder, alpha-cellulose, flax fiber element, grass fiber element, paper grade (stock) pulpboard etc. in addition.
4. the preparation method of acetylize nano cellulose crystal according to claim 1, is characterized in that adopted solvent system is the anhydrous phosphoric acid system being mixed by polyphosphoric acid and phosphoric acid solution, P
2o
5content is 70%～85%.
5. the preparation method of acetylize nano cellulose crystal according to claim 1, the mass ratio that it is characterized in that cellulosic material described in step 1 and anhydrous phosphoric acid system is 0.04～0.80:1.
6. the preparation method of acetylize nano cellulose crystal according to claim 1, is characterized in that the dispersion condition described in step 1 is: at temperature-20 DEG C～65 DEG C of temperature, mediate or be stirred to colloidal sol shape.
7. the preparation method of acetylize nano cellulose crystal according to claim 1, the mass ratio that it is characterized in that the add-on of diacetyl oxide described in step 2 and cellulosic material is 0.3～30.0:1.
8. the preparation method of acetylize nano cellulose crystal according to claim 1, is characterized in that described in step 2, acetylation reagent is not limited to diacetyl oxide, can also be Acetyl Chloride 98Min., acetyl bromide, acetic acid etc.
9. the preparation method of acetylize nano cellulose crystal according to claim 1; it is characterized in that the reaction described in step 2 is preferably acetylize; but be not limited to acetylize; can also be propionyl, Butyrylation, maleylation, bay acidylate, grease acidylate, benzoylation, oxalyl etc.; obtaining corresponding product is the nano cellulose crystal of propionyl, Butyrylation, maleylation, bay acidylate, grease acidylate, benzoylation, oxalyl, be respectively corresponding acid anhydrides, carboxylic acid halides or acid to the acylating reagent being applied to.
10. the preparation method of acetylize nano cellulose crystal according to claim 1, is characterized in that the temperature of reaction described in step 2 is 0 DEG C～60 DEG C, and the reaction times is 10min～24h.
The preparation method of 11. acetylize nano cellulose crystals according to claim 1; the acetylize nano cellulose crystal that it is characterized in that preparation belongs to cellulose Ⅱ type structure; crystal diameter is about 3nm～10nm, and length is about 30nm～500nm, and length-to-diameter ratio is about 10-50.
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| CN201310061123.1A CN104004101A (en) | 2013-02-27 | 2013-02-27 | Preparation method for acetylated nanocellulose crystal |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601754A (en) * | 2016-01-06 | 2016-05-25 | 扬州大学 | Preparing method for acylated fiber nanocrystal |
| CN105713100A (en) * | 2016-03-16 | 2016-06-29 | 东北林业大学 | Method for rapidly preparing cellulose nanocrystalline |
| CN106749684A (en) * | 2016-11-16 | 2017-05-31 | 江南大学 | A kind of malic acid is esterified the preparation method of nano-cellulose |
| CN109096406A (en) * | 2018-10-25 | 2018-12-28 | 河北农业大学 | A kind of II type nanocrystal cellulose ester and its preparation process and purposes |
| CN109517863A (en) * | 2018-12-06 | 2019-03-26 | 武汉科丝力纤维制造有限公司 | A kind of preparation method of modified hydrophilic group nano cellulose crystal |
| WO2019105287A1 (en) * | 2017-12-01 | 2019-06-06 | 济南圣泉集团股份有限公司 | Nanocellulose, preparation method therefor and use thereof |
| CN110498934A (en) * | 2019-09-04 | 2019-11-26 | 江苏理工学院 | A kind of method of cellulose derivative control Pickering emulsion particle diameter |
| CN115141378A (en) * | 2022-06-28 | 2022-10-04 | 南京塑净新材料科技有限公司 | Special efficient nucleating agent for surface acetylation nano cellulose crystal grafted polylactic acid and preparation method and application thereof |
| CN115246888A (en) * | 2022-09-23 | 2022-10-28 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method of hydrophobic nanocellulose |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601754A (en) * | 2016-01-06 | 2016-05-25 | 扬州大学 | Preparing method for acylated fiber nanocrystal |
| CN105601754B (en) * | 2016-01-06 | 2017-10-17 | 扬州大学 | A kind of preparation method of acylated cellulose nanocrystal |
| CN105713100A (en) * | 2016-03-16 | 2016-06-29 | 东北林业大学 | Method for rapidly preparing cellulose nanocrystalline |
| CN106749684A (en) * | 2016-11-16 | 2017-05-31 | 江南大学 | A kind of malic acid is esterified the preparation method of nano-cellulose |
| WO2019105287A1 (en) * | 2017-12-01 | 2019-06-06 | 济南圣泉集团股份有限公司 | Nanocellulose, preparation method therefor and use thereof |
| CN109096406A (en) * | 2018-10-25 | 2018-12-28 | 河北农业大学 | A kind of II type nanocrystal cellulose ester and its preparation process and purposes |
| CN109517863A (en) * | 2018-12-06 | 2019-03-26 | 武汉科丝力纤维制造有限公司 | A kind of preparation method of modified hydrophilic group nano cellulose crystal |
| CN110498934A (en) * | 2019-09-04 | 2019-11-26 | 江苏理工学院 | A kind of method of cellulose derivative control Pickering emulsion particle diameter |
| CN115141378A (en) * | 2022-06-28 | 2022-10-04 | 南京塑净新材料科技有限公司 | Special efficient nucleating agent for surface acetylation nano cellulose crystal grafted polylactic acid and preparation method and application thereof |
| CN115141378B (en) * | 2022-06-28 | 2024-01-19 | 南京塑净新材料科技有限公司 | Special efficient nucleating agent for surface acetylated nanocellulose crystal grafted polylactic acid and preparation method and application thereof |
| CN115246888A (en) * | 2022-09-23 | 2022-10-28 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method of hydrophobic nanocellulose |
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Application publication date: 20140827 |