CN103881117A - Method for preparing surface-functionalized cellulose nanospheres - Google Patents
Method for preparing surface-functionalized cellulose nanospheres Download PDFInfo
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Abstract
The present invention relates to a method for preparing surface-functionalized cellulose nanospheres, which comprises (1) adding cellulosic fibers to the alkali liquor, swelling, filtering the solution, washing the product with water for several times until pH is 7, and drying to constant weight; (2) then adding the above product into mixed acid for fully infiltrating, reacting the above solution under stirring for 2-10 hours at 60-90 DEG C, naturally cooling the reaction products, adding an alkali solution until the pH of the solution is adjusted to 7 to obtain a dispersion liquid of cellulose nanospheres, then centrifuging the dispersion liquid, washing with water for three times, carrying out ultrasonic treatment, and then carrying out freeze drying to constant weight to obtain a cellulose nanospheres. The preparation method has advantages of low raw material cost, simple preparation process and mild preparation conditions; the surfaces of the cellulose nanospheres have functional groups, so that thermal stability and hydrophobicity are improved, self-aggregation is reduced, dispersion is easy, size is small, distribution is narrow, control is easy, specific surface area is large, reactivity is high and etc.
Description
Technical field
The invention belongs to the nanocrystalline preparation field of Mierocrystalline cellulose, particularly a kind of preparation method of surface-functionalized cellulose nanospheres.
Background technology
Due to the high length-diameter ratio of Mierocrystalline cellulose nano whisker or nanocrystal, good mechanical property, degradable and reproducible characteristic; their use has been proposed as the main component of the biomaterial of development of new cheapness (Sturcova A; Davies GR, Eichhorn SJ. Elastic modulus and stress-transfer properties of tunicate cellulose whiskers. Biomacromolecules 2005; 6:1055-1061.).If compared with other inorganic reinforcing filler, for biological polymer, due to the nanocrystalline non-attrition process performance of Mierocrystalline cellulose, allow high filler content and significant cost savings, they have some other advantages, comprise their Resource Availabilities widely, less energy-consumption, be easy to reclaim and comprise burning, high sound attenuation and quite simple processing characteristics (Samir MASA, Dufresne A. Review of recent research into cellulosic whiskers their properties and their application in nanocomposite field. Biomacromolecules 2005, 6:612-626.).Mierocrystalline cellulose is nanocrystalline is mainly divided into two kinds, bar-shaped and spherical.Rod-like fibre element is nanocrystalline because its good machinery, heat and barrier property are acknowledged as a kind of important bio-based filler, for strengthening machinery and the barrier property of biological polymer, but it also exists some shortcomings, disperse such as being difficult in polymkeric substance, nucleating effect is not remarkable etc.Cellulose nanospheres has many-sided good characteristic, as little in size, good biocompatibility, biodegradable, degree of crystallinity advantages of higher.Compared with nanocrystalline with common rod-like fibre element, cellulose nanospheres has larger specific surface area, surface has abundant activity hydroxy, be easier to the surface modification of nanometer ball, but because it does not have length-to-diameter ratio, the machinery to matrix material and the raising of barrier property are again be not as nanocrystalline as rod-like fibre element.
The preparation method of cellulose nanospheres is by out (Wang N of Cheng research group reported first at present; Ding EY, Cheng RS. Preparation and liquid crystalline properties of spherical cellulose nanocrystals. Langmuir 2008; 24:5-8.), they adopt the nitration mixture of inorganic acid to process Microcrystalline Cellulose, repeatedly centrifugal, dialysis, and vacuum-drying, obtains this cellulose nanospheres; Not enough is this complicated process of preparation, and aftertreatment is loaded down with trivial details.After have again investigator to adopt enzymolysis process, the preparation methods such as sulfuric acid process and sulfuric acid mixed acid process prepare cellulose nanospheres, but these methods all exist some problems, such as enzymolysis process long reaction time, productive rate is low, complicated (the Satyamurthy P that waits of reaction unit, Vigneshwaran N, A novel process for synthesis of spherical nanocellulose by controlled hydrolysis of microcrystalline cellulose using anaerobic microbial consortium. Enzyme and Microbial Technology 2013, 52:20-25).And the inadequate homogeneous of cellulose nanospheres size that every use adds the method for sulfuric acid solution to obtain; and surface is all with sulfate radical; cause its thermostability to reduce (Xiong R; Zhang XX; Tian D; Zhou ZH, Lu CH. Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics. Cellulose 2012; 19:1189-1198 Wang N, Ding EY, Cheng RS. Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups. Polymer 2007; 48:3486-3493).Thereby functionalization is carried out in the surface of cellulose nanospheres seem particularly important, and we adopt " Fischer esterification process ", with volatility acid solution acidolysis cellulosic fibre, make size stable homogeneous and the surface cellulose nanospheres with functional groups such as ester group, amide group, aldehyde radicals, both avoided because cause its thermostability to reduce with sulfate groups, reduce again the hydrogen bond action between nanometer ball, weakened its self aggregation phenomenon.
It is swelling that Qin Zongyi etc. are first placed in alkali lye by waste dissolvable fibers, be placed in again acid solution and carry out acidolysis, finally by crossing pH regulator, the processing such as lyophilize, make cellulose nanospheres (application number: 201110199585.0), they are first placed in alkali lye by cellulosic material again and soak afterwards, then immerse in oxidisability salt brine solution and react, products therefrom, through filtration, washing, lyophilize, has obtained a kind of carboxylated cellulose nanospheres (application number: 201210435306.0).The present invention adopts " Fischer esterification process ", with volatility acid solution acidolysis cellulosic fibre and it is carried out to surface esterification, make the cellulose nanospheres surface making with function group such as ester group, amide group, aldehyde radical, carboxyls, both improved the hydrophobicity of nanometer ball, make it be easier to disperse in hydrophobic polymer, improve again its high thermal stability, made the size of nanometer ball can keep stable homogeneous.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of surface-functionalized cellulose nanospheres, the method is undertaken surface-functionalized by cellulose nanospheres, the present invention preparation method used is simple and efficient, desired raw material is with low cost to be easy to get, the pharmaceutical chemicals using is volatile acid and alkali, with low cost and remove simple; The gentle easily control of preparation condition, is suitable for commercial scale production; Prepared Mierocrystalline cellulose is nanocrystalline to be had the little and narrowly distributing of size, size and is easy to that regulation and control, specific surface area are large, reactive behavior advantages of higher, it is a kind of Biodegradable material with very strong application potential, effectively carry out surface-functionalized to cellulose nanospheres, the nanometer ball hydrophobicity making is improved, be easier to disperse in hydrophobic polymer, and improve again its high thermal stability, made the size of nanometer ball can keep stable homogeneous.
The preparation method of a kind of surface-functionalized cellulose nanospheres of the present invention, comprising:
(1) cellulosic fibre being added to concentration is swelling 1-10 h in the alkali lye of 1-4mol/L, and wherein the mass volume ratio of fiber and alkali lye is 0.01-0.2 g/mL, and afterwards by above-mentioned solution filter, product is washed repeatedly, until PH=7, at 50-80
ounder C, be dried to constant weight;
(2) subsequently above-mentioned product being added to concentration is fully to infiltrate in the volatility mixed acid solution of 1-10 mol/L, and wherein the mass volume ratio of fiber and mixed acid solution is 0.002-0.02 g/mL, afterwards by above-mentioned solution at 60-90
ostirring reaction 2-10 h under C, after above-mentioned reaction product naturally cooling, adds alkaline solution, the pH value of solution is adjusted to 7, obtains cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, lyophilize, to constant weight, obtains cellulose nanospheres again.
Cellulosic fibre in described step (1) is Lyocell fiber, microcrystalline cellulose cellulose fiber or discarded cotton fibre.
Alkali lye in described step (1) is sodium hydroxide solution, aqua calcis, barium hydroxide solution or potassium hydroxide solution.
In described step (1), the swelling of described fiber at room temperature carries out.
Nitration mixture in described step (2) be hydrochloric acid respectively with formic acid, acetic acid, citric acid, oxalic acid or nitric acid in a kind of be prepared from contain two kinds of sour mixed acid solutions, the concentration of two kinds of acid solutions is 1-10mol/L, and hydrochloric acid and volume ratio that another is sour are 1:9.
Alkaline solution in described step (2) is ammonia soln, hydrazine hydrate solution or sodium hydroxide solution, and concentration is 1-4 mol/L.
In described step (2), the particle diameter of gained cellulose nanospheres is 10～150 nm.
Beneficial effect
(1) the present invention successfully uses " Fischer esterification process " to prepare surface-functionalized cellulose nanospheres, and the preparation technology who proposes is simple and easy to operate, and desired raw material is with low cost to be easy to get, and the pharmaceutical chemicals of use is acid and the alkali of commonly using, with low cost and remove simple; The gentle easily control of whole preparation condition, do not need expensive equipment, without cellulose nanospheres dispersion liquid being carried out to dialysis processing consuming time, only need direct lyophilize just can prepare cellulose nanospheres, greatly shorten preparation cycle and reduced production cost, being suitable for commercial scale production;
(2) the present invention adopts " Fischer esterification process " prepared cellulose nanospheres, for surface band has the controlled spherical nanocrystal of functionalization group, overcome the defect that other preparation methods of cellulose nanospheres exist, and there is the little and narrowly distributing of size, size and be easy to that regulation and control, specific surface area are large, reactive behavior advantages of higher, can be used as a kind of biomaterial that has application potential, it is at Preen nono matrix material, and there is application prospect more widely in the fields such as food, medicine, makeup, coating.
Accompanying drawing explanation
Fig. 1 is size distribution figure and the transmissioning electric mirror test shape appearance figure of cellulose nanospheres.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
It is in the aqua calcis of 1mol/L that microcrystalline cellulose cellulose fiber is added to concentration, swelling 4 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.02 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,50
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 2 mol/L and mix acid liquor that formic acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.008 g/mL, above-mentioned solution is packed in reaction vessel, in 65
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 6 h, after above-mentioned reaction product naturally cooling, add 2mol/L ammonia soln, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 10～35 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Embodiment 2
It is in the sodium hydroxide solution of 2mol/L that lyocell fiber is added to concentration, swelling 6 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.1 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,75
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 5 mol/L and mix acid liquor that formic acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.016 g/mL, above-mentioned solution is packed in reaction vessel, in 75
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 8 h, after above-mentioned reaction product naturally cooling, add 3mol/L hydrazine hydrate, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 30～55 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Embodiment 3
It is in the barium hydroxide solution of 1mol/L that discarded cotton fibre is added to concentration, swelling 4 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.04 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,65
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 7 mol/L and mix acid liquor that acetic acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.012 g/mL, above-mentioned solution is packed in reaction vessel, in 70
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 7 h, after above-mentioned reaction product naturally cooling, add 1mol/L sodium hydroxide solution, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 60～100 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Embodiment 4
It is in the potassium hydroxide solution of 1mol/L that microcrystalline cellulose cellulose fiber is added to concentration, swelling 7 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.12 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,70
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 5 mol/L and mix acid liquor that nitric acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.014 g/mL, above-mentioned solution is packed in reaction vessel, in 85
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 4 h, after above-mentioned reaction product naturally cooling, add 3mol/L ammonia soln, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 55～90 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Embodiment 5
It is in the aqua calcis of 1mol/L that Loycell fiber is added to concentration, swelling 4 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.02 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,60
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 4 mol/L and mix acid liquor that nitric acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.008 g/mL, above-mentioned solution is packed in reaction vessel, in 65
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 6 h, after above-mentioned reaction product naturally cooling, add 2mol/L hydrazine hydrate, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 45～75 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Embodiment 6
It is in the aqua calcis of 4mol/L that discarded cotton fibre is added to concentration, swelling 9 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.16 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,55
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 8 mol/L and mix acid liquor that oxalic acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.004 g/mL, above-mentioned solution is packed in reaction vessel, in 85
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 8 h, after above-mentioned reaction product naturally cooling, add 4mol/L sodium hydroxide, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 75～110 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Embodiment 7
It is in the sodium hydroxide solution of 3mol/L that microcrystalline cellulose cellulose fiber is added to concentration, swelling 5.5 h under room temperature, and wherein the mass volume ratio of fiber and alkali lye is 0.14 g/mL, and above-mentioned mixed solution is filtered, product is washed repeatedly, until PH=7,70
ounder C, be dried to constant weight; Subsequently above-mentioned product being added to concentration is respectively fully to infiltrate in the hydrochloric acid of 3 mol/L and mix acid liquor that formic acid is mixed to get in the ratio of 1:9, and wherein the mass volume ratio of fiber and acid solution is 0.01 g/mL, above-mentioned solution is packed in reaction vessel, in 80
ounder C, under stirring, tetrafluoroethylene stirring rake reacts 5 h, after above-mentioned reaction product naturally cooling, add 1mol/L ammonia soln, the pH value of solution is adjusted to 7, must be uniformly distributed cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, nano particle size is 50～70 nm with potentiometric analyzer mensuration cellulose nanospheres size distribution.By dispersion liquid lyophilize, can prepare the comparatively surface-functionalized cellulose nanospheres of homogeneous of high purity, size.
Claims (7)
1. a preparation method for surface-functionalized cellulose nanospheres, comprising:
(1) cellulosic fibre being added to concentration is swelling 1-10 h in the alkali lye of 1-4mol/L, and wherein the mass volume ratio of fiber and alkali lye is 0.01-0.2 g/mL, and afterwards by above-mentioned solution filter, product is washed repeatedly, until PH=7, at 50-80
ounder C, be dried to constant weight;
(2) subsequently above-mentioned product is added in nitration mixture fully and infiltrate, wherein the mass volume ratio of fiber and nitration mixture is 0.002-0.02 g/mL, afterwards by above-mentioned solution at 60-90
ostirring reaction 2-10 h under C, after above-mentioned reaction product naturally cooling, adds alkaline solution, the pH value of solution is adjusted to 7, obtains cellulose nanospheres dispersion liquid, then by ultrasonic 5-10 minute after centrifugal dispersion liquid washing three times, lyophilize, to constant weight, obtains cellulose nanospheres again.
2. the preparation method of a kind of surface-functionalized cellulose nanospheres according to claim 1, is characterized in that: the cellulosic fibre in described step (1) is Lyocell fiber, microcrystalline cellulose cellulose fiber or discarded cotton fibre.
3. the preparation method of a kind of surface-functionalized cellulose nanospheres according to claim 1, is characterized in that: the alkali lye in described step (1) is sodium hydroxide solution, aqua calcis, barium hydroxide solution or potassium hydroxide solution.
4. the preparation method of a kind of surface-functionalized cellulose nanospheres according to claim 1, is characterized in that: in step (1), the swelling of described fiber at room temperature carries out.
5. the preparation method of a kind of surface-functionalized cellulose nanospheres according to claim 1, it is characterized in that: the nitration mixture in described step (2) be hydrochloric acid respectively with formic acid, acetic acid, citric acid, oxalic acid or nitric acid in a kind of be prepared from contain two kinds of sour mixed acid solutions, the concentration of two kinds of acid solutions is 1-10mol/L, and hydrochloric acid and volume ratio that another is sour are 1:9.
6. the preparation method of a kind of surface-functionalized cellulose nanospheres according to claim 1, is characterized in that: the alkaline solution in described step (2) is ammonia soln, hydrazine hydrate solution or sodium hydroxide solution, and concentration is 1-4 mol/L.
7. the preparation method of a kind of surface-functionalized cellulose nanospheres according to claim 1, is characterized in that: in described step (2), the particle diameter of gained cellulose nanospheres is 10～150 nm.
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