CN1470532A - Surface modifier of ultrafin and nano mcirocrystal cellulose - Google Patents
Surface modifier of ultrafin and nano mcirocrystal cellulose Download PDFInfo
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- CN1470532A CN1470532A CNA031268250A CN03126825A CN1470532A CN 1470532 A CN1470532 A CN 1470532A CN A031268250 A CNA031268250 A CN A031268250A CN 03126825 A CN03126825 A CN 03126825A CN 1470532 A CN1470532 A CN 1470532A
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Abstract
The present invention relates to a surface modifying material of superfine and nano microcrystal cellulose and its production method. Said modifying material particle size is 6.5nm-500 micrometers, and its surface can be modified by means of acetic acid esterification. Its production method includes: in the liquid dispersion medium, under the action of acid catalyst the superfine and nano microcrystal cellulose and acid anhydride are reacted to make acetic acid esterification modification of the surface, then undergone the processes of washing, filtering and drying to obtain the surface modifying material, in which the volume ratio of liquid dispersion medium and superfine and nano microcrystal cellulose is 10-25:1 and the mass ratio of catalyst, acid anhydride and superfine and nano microcrystal cellulose is 0.5-15:1-25:100.
Description
Technical field the present invention relates to surface modification thing of ultra-fine and nano micro crystal cellulose and preparation method thereof.
Technical background is ultra-fine and nano micro crystal cellulose is very little owing to particle grain size, generally between 6.5nm～500 μ m, the long-pending sharply increase of specific grain surface this moment, the granule surface activity group increases, and the microcrystalline cellulose that its chemical reactivity is more general has have large increase.And because surface effects, ultra-fine and nano micro crystal cellulose can be scattered in the suitable medium steadily in the long term, forms accurate colloidal dispersion or colloidal dispersion, and its reactive behavior and homogeneity can obviously improve.By chemically modified is carried out on its surface, many new rerum naturas can appear, can obtain the product of character excellence with this.Crystallization ultra-fine and nano micro crystal cellulose is all very high, so have good physicals and mechanical property, can be used as filler particles etc. and is used.Therefore yet the ultra-fine and nano micro crystal cellulose and the common plastics consistency of non-modified are bad, are difficult to be used for composite filled with common plastics as filler.Therefore, need carry out modification, and modifier can not destroy physical and mechanical property ultra-fine and that the nano micro crystal cellulose inherent is good to ultra-fine and nano micro crystal cellulose.
Summary of the invention task of the present invention just provides a kind of surface modification thing of ultra-fine and nano micro crystal cellulose, this modifier is the good physical and mechanical property that has of maintenance itself not only, its lipophilicity has had tangible improvement before than modification, improve the consistency with macromolecular material widely, widened its Application Areas.
Another task of the present invention provides the preparation method of this surface modification thing, this method mild condition, and raw material is easy to get, and is simple to operate.
Ultra-fine and nano micro crystal cellulose surface modification thing provided by the invention, its size of particles are between 6.5nm～500 μ m, and the surface is through the acetic acid esterification modification.This modifier particle profile is bar-shaped or the ellipsoid shape, and whole microcrystal grain inside still keeps crystalline state.
The wherein ultra-fine and preferred 30nm of nano micro crystal cellulose surface modification thing size of particles～200 μ m.
The preparation method of this surface modification thing is in liquid dispersion medium, under the acid catalyst effect, carry out surperficial acetic acid esterification modification 6.5nm～500 μ m are ultra-fine with nano micro crystal cellulose and anhydride reaction, make through washing, filtration and drying, wherein liquid dispersion medium and ultra-fine and volume ratio nano micro crystal cellulose are 10～25: 1, the mass ratio of catalyzer, aceticanhydride and ultra-fine and nano micro crystal cellulose is 0.5～15: 1～25: 100, temperature of reaction is 30～80 ℃, and the reaction times is 1.5～6 hours.
Liquid dispersion medium can be selected from the mixed dispersion liquid of one or more different proportionings in water, trichloromethane, methylene dichloride, trichloroethane, ethylene dichloride, benzene,toluene,xylene, the tetracol phenixin.
Acid catalyst can be selected from the mixing acid of one or more different proportionings in methylsulphonic acid, sulfuric acid, perchloric acid, hydrochloric acid, phosphoric acid and the organic sulfonic acid.
The mass ratio preferred 1～10: 3～20: 100 of catalyzer, aceticanhydride and ultra-fine and nano micro crystal cellulose.
Preferred 37～45 ℃ of temperature of reaction, preferred 2～3 hours of reaction times.
Reaction product can detect by infrared spectra, as at 1735cm
-1About have carbonyl peak to occur then representing Microcrystalline Cellulose modification, products therefrom is a product.Further detection can utilize elemental microanalysis method, Microcrystalline Cellulose C, O after the modification, the ratio of H element are compared with pure cellulose, the shared ratio of C rises, and O, the shared ratio of H two elements descend, and can calculate the modification degree of product according to the proportional meter of its element.
The invention provides a kind of modifier that the acetic acid esterification is carried out on ultra-fine and nano micro crystal cellulose surface.The characteristics of this modifier are exactly when changing ultra-fine and nano micro crystal cellulose surface physical property, have made full use of good physical and mechanical property ultra-fine and that the nanometer Celluloasun Microcrystallisatum itself has again.This modifier has just carried out modification to the surface of ultra-fine and nano micro crystal cellulose, the modification part only accounts for the very little part of whole Mierocrystalline cellulose, and do not destroy its internal crystal structure, thereby the physicals of ultra-fine and nano micro crystal cellulose itself and mechanical property have obtained good maintenance; Yet because the acetic acid esterification has been carried out on its surface, make its surface physical property that very big variation take place, widened its Application Areas.After acetic acid esterification surface modification, the lipophilicity of ultra-fine and nano micro crystal cellulose has had tangible improvement before than modification, has improved the consistency with macromolecular material widely.Therefore the ultra-fine and nano micro crystal cellulose after the modification can be used as macromolecular materials such as filler and plastics and carries out compound, ultra-fine and nano micro crystal cellulose not only can play certain enhancing, toughening effect at this moment, can also make full use of cellulosic biodegradability and make biodegradable plastic.
But adopt the method for general homogeneous system reaction, be difficult to be prepared into the surface modification thing of ultra-fine and nano micro crystal cellulose.The solvent that mainly is homogeneous system can dissolve the cellulose acetate that generates, and makes last product be dissolved in solvent system and forms solution, and product is difficult to obtain.Destroy its internal crystal structure again easily by regenerated from washing, thereby destroyed mechanical property and physicals ultra-fine and that nano micro crystal cellulose itself is good.Therefore the invention provides a kind of method of the microcrystalline cellulose surface being carried out modification by the nonhomogeneous system method.This method has overcome the above-mentioned shortcoming of homogeneous system, in the entire reaction course, ultra-fine and nano micro crystal cellulose is to be suspended in the liquid dispersion medium with particulate state, just can obtain product by the simple filtering method, and is beneficial to very much the recovery of liquid dispersion medium.The advantage of this method is:
1, when changing ultra-fine and nano micro crystal cellulose surface physical property, do not destroy its internal crystal structure again, thereby make the premium properties of Microcrystalline Cellulose own obtain maintenance.
2, can change different reaction systems according to actual needs,, thereby change the surface physical property of ultra-fine and nano micro crystal cellulose, produce needs, widen its application prospect to satisfy to the ultra-fine and surperficial modification of carrying out different systems of nano micro crystal cellulose.
3, the surface physical property of modifier can be regulated by the amount of control reactant according to actual needs, to meet the different needs convenience very.When for example ultra-fine and nano micro crystal cellulose being carried out surface modification,, come control surface modification degree, make itself and the consistency of every kind of plastics all reach the best by the amount of control diacetyl oxide at the different characteristic of various plastics with diacetyl oxide.
4, because modifier is insoluble to liquid dispersion medium, product is easy to obtain, and helps the recovery of liquid dispersion medium, has reduced production cost.
5, the product after the modification has biodegradability, therefore can be used for preparing biodegradable plastic.
6, this method mild condition, raw material is easy to get, and is simple to operate.
To ultra-fine and surface nano micro crystal cellulose carrying out the acetic acid esterification modification, through washing, filter and the resulting product in dry back, change has taken place in its surperficial amphipathic property, can obviously improve the consistency between itself and the lipophilicity material.Because the internal crystallization structure of Microcrystalline Cellulose is constant substantially after the modification, so it still keeps good mechanics mechanical property, can be used as functional filler and is widely used in the industries such as plastics, rubber, coating.
Preferred forms
Embodiment 1
Get Microcrystalline Cellulose 2.0g, median size is 90 μ m.Add the 30ml trichloroethane, stir, mix and add diacetyl oxide 1.0ml, sulfuric acid 0.03ml reacted 2 hours, and whole process control temp is 35 ℃.Hypsokinesis goes out suspension in funnel, and washing is to neutral, and oven dry promptly obtains product.
Embodiment 2
Get Microcrystalline Cellulose 2.0g, median size is 10 μ m.Add 30ml dimethylbenzene, stir, mix and add diacetyl oxide 0.1ml, sulfuric acid 0.03ml reaches, and answers 2 hours, and whole process control temp is 37 ℃.Hypsokinesis goes out suspension in funnel, and after the washing, oven dry promptly obtains product.
Embodiment 3
Get Microcrystalline Cellulose 3.0g, median size is 1.0 μ m.Add distilled water 50ml, stir for some time, treat that Microcrystalline Cellulose is dispersed in the water after, add diacetyl oxide 0.5ml, sulfuric acid 0.05ml.Controlled temperature is 40 ℃ in the reaction process, reacts 6 hours.With the product filtration washing, oven dry promptly gets product.
Embodiment 4
Get Microcrystalline Cellulose 2.0g, median size is 50nm.Add 40ml dimethylbenzene, stir, mix and add diacetyl oxide 0.4ml, methylsulphonic acid 0.1ml and a small amount of dimethylbenzene reacted 3 hours, and whole process control temp is 50 ℃.With the product filtration washing, oven dry promptly gets product.
Embodiment 5
Get Microcrystalline Cellulose 3.0g, median size is 100nm.Add 35ml toluene, stir, mix and add diacetyl oxide 0.03ml, methylsulphonic acid 0.30ml and 5ml toluene were in 75 ℃ of back flow reaction 4 hours.With the product filtration washing, oven dry promptly gets product.
Claims (7)
1, a kind of ultra-fine and nano micro crystal cellulose surface modification thing, its size of particles are between 6.5nm～500 μ m, and the surface is through the acetic acid esterification modification.
2, the ultra-fine and nano micro crystal cellulose surface modification thing of claim 1, wherein size of particles is 30nm～200 μ m.
3, the preparation method of claim 1 or 2 ultra-fine and nano micro crystal cellulose surface modification thing, be in liquid dispersion medium, under the acid catalyst effect, carry out surperficial acetic acid esterification modification 6.5nm～500 μ m are ultra-fine with nano micro crystal cellulose and anhydride reaction, through washing, filter with drying and make, wherein liquid dispersion medium and ultra-fine and volume ratio nano micro crystal cellulose are 10～25: 1, catalyzer, aceticanhydride and ultra-fine and mass ratio nano micro crystal cellulose are 0.5～15: 1～25: 100, temperature of reaction is 30～80 ℃, and the reaction times is 1.5～6 hours.
4, the method for claim 3, wherein liquid dispersion medium is selected from the mixed dispersion liquid of one or more different proportionings in water, trichloromethane, methylene dichloride, trichloroethane, ethylene dichloride, benzene,toluene,xylene, the tetracol phenixin.
5, claim 3 or 4 method, wherein acid catalyst is selected from the mixing acid of one or more different proportionings in methylsulphonic acid, sulfuric acid, perchloric acid, hydrochloric acid, phosphoric acid and the organic sulfonic acid.
6, claim 3 or 4 method, wherein the mass ratio of catalyzer, aceticanhydride and ultra-fine and nano micro crystal cellulose is 1～10: 3～20: 100.
7, claim 3 or 4 method, wherein temperature of reaction is 37～45 ℃, the reaction times is 2～3 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03126825 CN1209375C (en) | 2003-06-12 | 2003-06-12 | Surface modifier of ultrafin and nano mcirocrystal cellulose |
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| CN 03126825 CN1209375C (en) | 2003-06-12 | 2003-06-12 | Surface modifier of ultrafin and nano mcirocrystal cellulose |
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| CN1470532A true CN1470532A (en) | 2004-01-28 |
| CN1209375C CN1209375C (en) | 2005-07-06 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006068611A1 (en) | 2004-12-23 | 2006-06-29 | Organoclick Ab | Modification of amines and alcohols |
| CN102080343A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Application of anion nano microcrystalline cellulose as paper reinforcer |
| CN102080342A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Anionic organic particles and preparation and application thereof |
| CN102080341A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Cationic organic particles and preparation and application thereof |
| CN102702361A (en) * | 2012-05-19 | 2012-10-03 | 吉林大学 | Esterification modification method of microcrystalline cellulose |
| CN103132169A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院理化技术研究所 | Preparation method for cellulose nano-fibers capable of dispersing stably |
| CN104220463A (en) * | 2012-03-29 | 2014-12-17 | Dic株式会社 | Method for producing modified cellulose nanofibers, modified cellulose nanofibers, resin composition, and molded body thereof |
| CN104245740A (en) * | 2012-10-05 | 2014-12-24 | 奥林巴斯株式会社 | Cellulose nanofiber and method for producing same, composite resin composition, and molded article |
| CN105131128A (en) * | 2015-09-24 | 2015-12-09 | 上海应用技术学院 | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents |
| CN105295063A (en) * | 2015-10-15 | 2016-02-03 | 安徽山河药用辅料股份有限公司 | Surface-modified microcrystalline cellulose and preparation method thereof |
| CN106167558A (en) * | 2015-05-20 | 2016-11-30 | 住友橡胶工业株式会社 | Rubber composition, rubber composition for tire and pneumatic tire |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
| CN107652448A (en) * | 2017-10-25 | 2018-02-02 | 黑龙江工程学院 | A kind of biomass micro mist surface modifying method using carbon suboxide as modifying agent |
| CN112940140A (en) * | 2021-01-29 | 2021-06-11 | 中国石油大学(华东) | Method for preparing super-air-wet nano microcrystalline cellulose by one-step method and application |
| CN114535865A (en) * | 2020-11-26 | 2022-05-27 | 海太半导体（无锡）有限公司 | Soldering paste for flip chip |
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2003
- 2003-06-12 CN CN 03126825 patent/CN1209375C/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006068611A1 (en) | 2004-12-23 | 2006-06-29 | Organoclick Ab | Modification of amines and alcohols |
| CN102080343B (en) * | 2010-11-25 | 2013-05-29 | 山东轻工业学院 | Application of anion nano microcrystalline cellulose as paper reinforcer |
| CN102080343A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Application of anion nano microcrystalline cellulose as paper reinforcer |
| CN102080342A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Anionic organic particles and preparation and application thereof |
| CN102080341A (en) * | 2010-11-25 | 2011-06-01 | 山东轻工业学院 | Cationic organic particles and preparation and application thereof |
| CN102080341B (en) * | 2010-11-25 | 2013-04-24 | 山东轻工业学院 | Cationic organic particles and preparation and application thereof |
| CN102080342B (en) * | 2010-11-25 | 2013-04-24 | 山东轻工业学院 | Anionic organic particles and preparation and application thereof |
| CN103132169B (en) * | 2011-11-30 | 2015-09-16 | 中国科学院理化技术研究所 | A kind of cellulose nano-fibrous preparation method of energy stable dispersion |
| CN103132169A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院理化技术研究所 | Preparation method for cellulose nano-fibers capable of dispersing stably |
| CN104220463B (en) * | 2012-03-29 | 2017-05-24 | Dic株式会社 | Method for producing modified cellulose nanofibers, modified cellulose nanofibers, resin composition, and molded body thereof |
| CN104220463A (en) * | 2012-03-29 | 2014-12-17 | Dic株式会社 | Method for producing modified cellulose nanofibers, modified cellulose nanofibers, resin composition, and molded body thereof |
| CN102702361A (en) * | 2012-05-19 | 2012-10-03 | 吉林大学 | Esterification modification method of microcrystalline cellulose |
| CN102702361B (en) * | 2012-05-19 | 2014-03-19 | 吉林大学 | Esterification modification method of microcrystalline cellulose |
| CN104245740A (en) * | 2012-10-05 | 2014-12-24 | 奥林巴斯株式会社 | Cellulose nanofiber and method for producing same, composite resin composition, and molded article |
| CN106167558B (en) * | 2015-05-20 | 2020-07-31 | 住友橡胶工业株式会社 | Rubber composition, rubber composition for tire, and pneumatic tire |
| CN106167558A (en) * | 2015-05-20 | 2016-11-30 | 住友橡胶工业株式会社 | Rubber composition, rubber composition for tire and pneumatic tire |
| CN105131128A (en) * | 2015-09-24 | 2015-12-09 | 上海应用技术学院 | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents |
| CN105295063A (en) * | 2015-10-15 | 2016-02-03 | 安徽山河药用辅料股份有限公司 | Surface-modified microcrystalline cellulose and preparation method thereof |
| CN105295063B (en) * | 2015-10-15 | 2019-01-11 | 安徽山河药用辅料股份有限公司 | A kind of surface modification of microcrystalline cellulose and preparation method thereof |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
| CN107652448A (en) * | 2017-10-25 | 2018-02-02 | 黑龙江工程学院 | A kind of biomass micro mist surface modifying method using carbon suboxide as modifying agent |
| CN107652448B (en) * | 2017-10-25 | 2019-09-24 | 黑龙江工程学院 | It is a kind of using carbon suboxide as the biomass micro mist surface modifying method of modifying agent |
| CN114535865A (en) * | 2020-11-26 | 2022-05-27 | 海太半导体（无锡）有限公司 | Soldering paste for flip chip |
| CN112940140A (en) * | 2021-01-29 | 2021-06-11 | 中国石油大学(华东) | Method for preparing super-air-wet nano microcrystalline cellulose by one-step method and application |
| CN112940140B (en) * | 2021-01-29 | 2022-03-11 | 中国石油大学(华东) | Method for preparing super-air-wet nano microcrystalline cellulose by one-step method and application |
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| CN1209375C (en) | 2005-07-06 |
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