CN111171582B - Preparation method of self-dispersed cellulose microgel - Google Patents
Preparation method of self-dispersed cellulose microgel Download PDFInfo
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The invention discloses a preparation method of self-dispersed cellulose microgel, which comprises the following steps: step 1, weighing raw materials: respectively weighing sodium hydroxide, urea, cellulose, gelatin and water; step 2, preparing a cellulose solution; step 3, preparing a gelatin solution; step 4, preparing a crude product of the cellulose microgel; and 5, dialyzing, self-dispersing, separating, and taking supernatant to obtain the cellulose microgel. The self-dispersible microgel is prepared in a green solvent sodium hydroxide/urea aqueous solution of cellulose, the used solvent is nontoxic, pollution-free and low in price, the preparation method is simple, the reaction can be carried out at normal temperature, the speed is high, and the yield is high. The coupling agent epichlorohydrin used in the invention can couple hydrophilic gelatin peptide chains to cellulose glucose chains, and meanwhile, a stable net structure is formed in a cellulose/gelatin system, so that the stability of the microgel and the film-forming water resistance of the microgel are enhanced on the premise of ensuring the dispersion of the microgel in water.
Description
Technical Field
The invention belongs to the technical field of preparation of cellulose gel, and relates to a preparation method of self-dispersed cellulose microgel.
Background
Cellulose is biomass polysaccharide with the most abundant content in nature, is derived from green plants such as cotton, hemp, straws, bagasse and other higher plants and marine organisms, and is considered as an inexhaustible energy source and chemical raw material in the future due to the advantages of low cost, biodegradability, good biocompatibility, easy modification and the like. However, the strong inter-molecular-chain hydrogen bonding network and the highly crystalline aggregated structure of cellulose itself, the fact that natural cellulose is insoluble in water and in general in organic and inorganic solvents, makes its processing extremely difficult, resulting in the very limited use of coating agents based on cellulose entities to date, so that only cellulose derivatives such as Cellulose Acetate (CA) and Nitrocellulose (NC) have been used in the coating agent field for a considerable period of time. CA. The NC coating has higher transparency and emulsion stability, and can be dispersed in water by introducing the polyurethane prepolymer containing hydrophilic groups, so that good film-forming performance is obtained, but the NC coating has few varieties and low industrialization degree, and a large amount of organic solvent is required in the water-based process, so that the full-water emulsion is not realized substantially. In addition, NC is poor in light resistance, easy to yellow, and high in CA price, which limits further widespread use thereof. Therefore, the development of novel all-biomass materials is urgently needed to expand the types of the coating agents and promote the development of the coating agents to the more environment-friendly field.
The appearance of an alkali/urea water system creates superior conditions for dissolving cellulose and preparing functional materials by modifying the cellulose in a homogeneous system; however, the dilution of the dissolved cellulose-alkali/urea aqueous solution with water immediately results in the formation of flocs without any strength, which greatly limits the application of cellulose in the industrial field. In order to make the cellulose dispersible in water even when the alkali/urea is removed, the cellulose must be chemically modified.
An excellent medium for the homogeneous etherification of cellulose in aqueous alkali/urea solutions due to the presence of alkali, in which a series of cellulose derivatives soluble in water or common solvents including methyl cellulose, ethyl cellulose, quaternized cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, etc. have been successfully obtained. However, the low molecular weight and high hygroscopicity of cellulose derivatives limit their large number of potential applications, leading to a weakening of their mechanical properties; the gelatin molecular structure has abundant hydrophilic groups of amino and carboxyl, and is introduced into the cellulose structure in a covalent polymerization manner, so that the gelatin molecular structure is an effective way for realizing the aqueous cellulose microgel.
Disclosure of Invention
The invention aims to provide a preparation method of self-dispersed cellulose microgel, which has the advantages of easily available raw materials, low price, no pollution, simple preparation steps, high stability of the prepared cellulose microgel and excellent film-forming water resistance.
The technical scheme adopted by the invention is as follows: a preparation method of self-dispersed cellulose microgel specifically comprises the following steps:
step 2, preparing a cellulose solution:
sequentially adding the weighed sodium hydroxide and urea into water to obtain a sodium hydroxide urea mixed solution, and precooling; then adding cellulose, and stirring to obtain a cellulose solution;
step 3, preparing a gelatin solution:
adding the weighed gelatin into water, and carrying out water bath to obtain a gelatin solution;
step 4, preparing a crude product of the cellulose microgel:
adding the gelatin solution obtained in the step (3) into the cellulose solution obtained in the step (2) and uniformly stirring, adding epoxy chloropropane while stirring, and stirring and reacting for 2-4 h to obtain a crude product of the cellulose microgel;
And (4) transferring the crude product of the cellulose microgel prepared in the step (4) into a dialysis bag for dialysis until the pH of the dialysate is neutral, taking out the product of the dialysis bag, adding water, stirring, standing, separating, and taking supernatant to obtain the cellulose microgel.
The present invention is also characterized in that,
in the step 2, the mass fraction of the cellulose in the cellulose solution is 3-5%.
In the step 2, the mass fraction of sodium hydroxide in the sodium hydroxide urea mixed solution is 7-8%, and the mass fraction of urea is 11-12%.
And (3) precooling the mixed solution of the sodium hydroxide and the urea to-12 to-5 ℃ in the step 2.
In the step 3, the mass fraction of the gelatin solution is 10-20%;
heating in water bath to 50-70 ℃, and carrying out water bath for 30-60 min.
In the step 4, the mass ratio of the gelatin to the cellulose solute is 1: 1-9.
And 4, the epoxy chloropropane is 6-10 times of the molar weight of the cellulose glucose unit in the cellulose.
Step 4, changing water every 6h during dialysis.
And (4) stirring at room temperature for 30-40 min, and standing for 24-48 h.
The invention has the beneficial effects that: the preparation method of the self-dispersible cellulose microgel provided by the invention can be used for preparing the self-dispersible microgel in a green solvent sodium hydroxide/urea aqueous solution of cellulose, and the used solvent is nontoxic, pollution-free, low in price, simple in preparation method, capable of reacting at normal temperature, high in speed and high in yield. The coupling agent epichlorohydrin used in the invention can couple hydrophilic gelatin peptide chains to cellulose glucose chains, and meanwhile, a stable net structure is formed in a cellulose/gelatin system, so that the stability of the microgel and the film-forming water resistance of the microgel are enhanced on the premise of ensuring the dispersion of the microgel in water. The prepared microgel has the size of nanoparticles of 80-150 nm and high stability, can be used in the fields of leather finishing, packaging materials and biological films, is a biocompatible and completely biodegradable environment-friendly material, and belongs to the field of sustainable development.
Drawings
FIG. 1 is a graph showing a particle size distribution of a cellulose microgel prepared in example 4 of a method for preparing a self-dispersed cellulose microgel according to the present invention;
FIG. 2 is a graph showing the variation in particle size stability of cellulose microgels prepared in examples 4 and 5, which are self-dispersing cellulose microgels of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of self-dispersed cellulose microgel, which comprises the following steps:
step 2, preparing a cellulose solution:
sequentially adding the weighed sodium hydroxide and urea into water to obtain a sodium hydroxide urea mixed solution, and precooling; then adding cellulose, and stirring to obtain a cellulose solution;
step 3, preparing a gelatin solution:
adding the weighed gelatin into water, and carrying out water bath to obtain a gelatin solution;
step 4, preparing a crude product of the cellulose microgel:
adding the gelatin solution obtained in the step (3) into the cellulose solution obtained in the step (2) and uniformly stirring, adding epoxy chloropropane while stirring, and stirring and reacting for 2-4 h to obtain a crude product of the cellulose microgel;
And (4) transferring the crude product of the cellulose microgel prepared in the step (4) into a dialysis bag for dialysis until the pH of the dialysate is neutral, taking out the product of the dialysis bag, adding water, stirring, standing, separating, and taking supernatant to obtain the cellulose microgel.
In the step 2, the mass fraction of the cellulose in the cellulose solution is 3-5%.
In the step 2, the mass fraction of sodium hydroxide in the sodium hydroxide urea mixed solution is 7-8%, and the mass fraction of urea is 11-12%.
And (3) precooling the mixed solution of the sodium hydroxide and the urea to-12 to-5 ℃ in the step 2.
In the step 3, the mass fraction of the gelatin solution is 10-20%;
heating in water bath to 50-70 ℃, and carrying out water bath for 30-60 min.
In the step 4, the mass ratio of the gelatin to the cellulose solute is 1: 1-9.
And 4, the epoxy chloropropane is 6-10 times of the molar weight of the cellulose glucose unit in the cellulose.
Step 4, changing water every 6h during dialysis.
And (4) stirring at room temperature for 30-40 min, and standing for 24-48 h.
Example 1
(1) Preparation of cellulose solution and gelatin solution
Quickly putting 3g of cellulose into a 7 wt% sodium hydroxide and 12 wt% urea aqueous solution which is precooled to-12 ℃ and 97g, and fully stirring to obtain a 3 wt% cellulose solution; 10g of gelatin granules are added into 90g of deionized water, heated in a water bath at 50 ℃ for 60min to obtain a 10 wt% gelatin solution.
(2) Preparation of crude product of cellulose microgel
Slowly adding 3.33g of gelatin aqueous solution into 100g of cellulose solution, uniformly stirring, slowly dropwise adding 10.33g of epichlorohydrin into the mixed homogeneous solution of cellulose/gelatin, and reacting at room temperature for 3 hours to obtain a crude product of the cellulose microgel.
(3) Dialysis-self-dispersion-separation
Transferring the crude product of the cellulose microgel to a dialysis bag with the molecular weight cutoff of 100000 Da for dialysis, changing water every 6h until the pH of the dialysate is neutral, taking out 50g of the product of the dialysis bag, adding 25g of water, stirring for 30min, rotating at the speed of 800r/min, standing for 24h, and separating and taking supernatant to obtain the self-dispersed cellulose microgel.
The obtained cellulose microgel had a protein content of 18.0% and an average particle size of 150 nm.
Example 2
(1) Preparation of cellulose solution and gelatin solution
Quickly putting 3.5g of cellulose into an aqueous solution of 96.5g of 8 percent sodium hydroxide and 11 percent urea which is precooled to-10 ℃, and fully stirring to obtain a 3.5 weight percent cellulose solution; 12g of gelatin granules were added to 88g of deionized water, heated in a water bath at 55 ℃ for 50min to give a 12 wt% gelatin solution.
(2) Preparation of crude product of cellulose microgel
And slowly adding 7.29g of gelatin aqueous solution into 100g of cellulose solution, uniformly stirring, slowly dropwise adding 14.06g of epichlorohydrin into the mixed homogeneous solution of cellulose/gelatin, and reacting at room temperature for 3 hours to obtain a crude product of the cellulose microgel.
(3) Dialysis-self-dispersion-separation
Transferring the crude product of the cellulose microgel to a dialysis bag with the molecular weight cutoff of 100000 Da for dialysis, changing water every 6h until the pH of the dialysate is neutral, taking out 50g of the product of the dialysis bag, adding 25g of deionized water, stirring for 30min, rotating at the speed of 800r/min, standing for 48h, separating and taking the supernatant to obtain the self-dispersed cellulose microgel.
The obtained cellulose microgel had a protein content of 18.7% and an average particle size of 120 nm.
Example 3
A method for preparing a self-dispersed microgel, comprising the steps of:
(1) preparation of cellulose solution and gelatin solution
Quickly putting 4.5g of cellulose into an aqueous solution of 8 percent of sodium hydroxide and 11 percent of urea which is precooled to-6 ℃ and is 95.5g, and fully stirring to obtain a cellulose solution with the weight percent of 4.5; 16g of gelatin granules were added to 84g of deionized water, heated in a water bath at 65 ℃ for 40min to give a 16 wt% gelatin solution.
(2) Preparation of crude product of cellulose microgel
Slowly adding 18.75g of gelatin aqueous solution into 100g of cellulose solution, uniformly stirring, slowly dropwise adding 23.25g of epichlorohydrin into the mixed homogeneous solution of cellulose/gelatin, and reacting at room temperature for 3h to obtain a crude product of the cellulose microgel.
(3) Dialysis-self-dispersion-separation
Transferring the crude product of the cellulose microgel to a dialysis bag with the molecular weight cutoff of 100000 Da for dialysis, changing water every 6h until the pH of the dialysate is neutral, taking out 50g of the product of the dialysis bag, adding 25g of deionized water, stirring for 40min, rotating at the speed of 800r/min, standing for 48h, separating and taking the supernatant to obtain the self-dispersed cellulose microgel.
The obtained cellulose microgel had a protein content of 30.8% and an average particle size of 90 nm.
Example 4
(1) Preparation of cellulose solution and gelatin solution
Quickly putting 4g of cellulose into 96g of 7% sodium hydroxide and 12% urea aqueous solution precooled to the temperature of minus 8 ℃, and fully stirring to obtain 4 wt% of cellulose solution; 14g of gelatin granules were added to 86g of deionized water, heated in a water bath at 60 ℃ for 45min to give a 14 wt% gelatin solution.
(2) Preparation of crude product of cellulose microgel
Slowly adding 12.24g of gelatin aqueous solution into 100g of cellulose solution, uniformly stirring, slowly dropwise adding 18.37g of epichlorohydrin into the mixed homogeneous solution of cellulose/gelatin, and reacting at room temperature for 3h to obtain a crude product of the cellulose microgel.
(3) Dialysis-self-dispersion-separation
Transferring the crude product of the cellulose microgel to a dialysis bag with the molecular weight cutoff of 100000 Da for dialysis, changing water every 6h until the pH of the dialysate is neutral, taking out 50g of the product of the dialysis bag, adding 25g of deionized water, stirring for 35min, rotating at the speed of 800r/min, standing for 36h, separating and taking supernatant to obtain the self-dispersed cellulose microgel.
As shown in fig. 1, the obtained cellulose microgel had a protein content of 24.1% and an average particle size of 87 nm; as shown in fig. 2, the particle size stability of the obtained vitamin microgel was measured.
Example 5
A method for preparing a self-dispersed microgel, comprising the steps of:
(1) preparation of cellulose solution and gelatin solution
Quickly putting 5g of cellulose into a 7% sodium hydroxide and 12% urea aqueous solution precooled to-5 ℃ and 95g of the cellulose, and fully stirring to obtain a 5 wt% cellulose solution; 20g of gelatin granules are added into 80g of deionized water, heated in a water bath at 70 ℃ and subjected to a water bath for 30min to obtain a 20 wt% gelatin solution.
(2) Preparation of crude product of cellulose microgel
Slowly adding 25g of gelatin aqueous solution into 100g of cellulose solution, uniformly stirring, slowly dropwise adding 28.70g of epoxy chloropropane into the mixed homogeneous solution of cellulose/gelatin, and reacting at room temperature for 2h to obtain a crude product of the cellulose microgel.
(3) Dialysis-self-dispersion-separation
Transferring the crude product of the cellulose microgel to a dialysis bag with the molecular weight cutoff of 100000 Da for dialysis, changing water every 6h until the pH of the dialysate is neutral, taking out 50g of the product of the dialysis bag, adding 25g of deionized water, stirring for 40min, rotating at the speed of 800r/min, standing for 48h, separating and taking the supernatant to obtain the self-dispersed cellulose microgel.
The protein content of the obtained cellulose microgel is 33.6 percent, and the average grain size is 120 nm; meanwhile, as shown in fig. 2, the stability of the obtained cellulose microgel was measured and compared with the stability of the cellulose microgel obtained in example 4.
As can be seen from fig. 1, the particle size of the cellulose microgel is concentrated at 80nm, and has a narrow particle size distribution, and the particle size of the cellulose microgel is uniform, and since gelatin itself contains abundant hydrophilic groups, the introduction of gelatin has two effects: first, the hydrophilicity of cellulose is enhanced; second, steric hindrance is created, weakening the hydrogen bonding. The two actions of the gelatin prevent the cellulose from being re-aggregated under the condition of removing the sodium hydroxide and urea mixed solution, so that the cellulose is promoted to be self-dispersed in water, and the cellulose microgel with uniform particle size is obtained.
As can be seen from fig. 2, the storage stability of the prepared self-dispersed cellulose microgel was not significantly different after 3 months of storage, indicating that the cellulose microgel has high storage stability for at least 3 months. The particle size has no obvious difference with the time, which shows that the microgel has high stability. The gelatin and the cellulose are covalently bonded together through the coupling agent, so that a stable net structure is formed in the system, and the microgel structure cannot be transformed into a macromolecular aggregate under certain external environment.
According to the preparation method, the cellulose is dissolved in the pre-cooled sodium hydroxide urea mixed solution to prepare the cellulose solution; adding gelatin into water, heating in water bath, and stirring to obtain gelatin solution; and then mixing the cellulose solution and the gelatin solution, stirring uniformly, adding a coupling agent epoxy compound, reacting at room temperature, dialyzing, self-dispersing, standing and separating to obtain the cellulose microgel. The adopted coupling agent epichlorohydrin can couple hydrophilic gelatin macromolecules to cellulose glucose chains, and simultaneously forms a stable reticular structure in a cellulose/gelatin system, so that the stability of the microgel and the film-forming water resistance of the microgel are enhanced on the premise of ensuring the dispersion of the microgel in water. By introducing the gelatin peptide chain onto the cellulose glucose chain, the prepared microgel has the size of nanoparticles of 80-150 nm and high stability, can be used in the fields of leather finishing, packaging materials and biological films, is a biocompatible and completely biodegradable environment-friendly material, and belongs to the field of sustainable development. The method is simple and easy to implement, and the preparation process does not adopt an organic solvent, so that the problem that the cellulose is difficult to disperse in water is solved.
Claims (3)
1. A preparation method of self-dispersed cellulose microgel is characterized by comprising the following steps:
step 1, weighing raw materials: respectively weighing sodium hydroxide, urea, cellulose, gelatin and water;
step 2, preparing a cellulose solution:
sequentially adding the weighed sodium hydroxide and urea into water to obtain a sodium hydroxide urea mixed solution, and precooling; then adding cellulose, and stirring to obtain a cellulose solution;
pre-cooling the mixed solution of sodium hydroxide and urea to-10 to-5 ℃;
the mass fraction of cellulose in the cellulose solution is 3-5%;
the mass fraction of sodium hydroxide in the sodium hydroxide urea mixed solution is 7% or 8%, and the mass fraction of urea is 11% or 12%;
step 3, preparing a gelatin solution:
adding the weighed gelatin into water, and carrying out water bath to obtain a gelatin solution;
the mass fraction of the gelatin solution is 10-20%;
heating in water bath to 50-70 ℃, and carrying out water bath for 30-60 min;
step 4, preparing a crude product of the cellulose microgel:
adding the gelatin solution obtained in the step (3) into the cellulose solution obtained in the step (2) and uniformly stirring, adding epoxy chloropropane while stirring, and stirring and reacting for 2-4 h to obtain a crude product of the cellulose microgel;
the mass ratio of the gelatin to the cellulose solute is 1: 1-9;
the epoxy chloropropane is 6-10 times of the molar weight of the cellulose glucose unit in the cellulose;
step 5, dialysis-self-dispersion-separation
And (4) transferring the crude product of the cellulose microgel prepared in the step (4) into a dialysis bag for dialysis until the pH of the dialysate is neutral, taking out the product of the dialysis bag, adding water, stirring, standing, separating, and taking supernatant to obtain the cellulose microgel.
2. The method of claim 1, wherein the dialysis of step 5 is performed with water change every 6 h.
3. The method for preparing self-dispersed cellulose microgel of claim 1, wherein in step 5, stirring is carried out for 30-40 min at room temperature, and standing is carried out for 24-48 h.
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| CN108641099A (en) * | 2018-04-25 | 2018-10-12 | 华南理工大学 | A kind of cellulose base responsive to temperature type conductive hydrogel and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB521446A (en) * | 1938-10-20 | 1940-05-22 | Frank Hartranft Reichel | Improvements in and relating to cellulose derivatives and to a process for producingthe same |
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2018
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| JPS6443501A (en) * | 1987-08-07 | 1989-02-15 | Nakahara Shokai Kk | Preparation of pectic acid-cellulose gel |
| CN102553545A (en) * | 2012-03-16 | 2012-07-11 | 川渝中烟工业有限责任公司 | Cellulose composite microsphere and preparation method thereof |
| CN108641099A (en) * | 2018-04-25 | 2018-10-12 | 华南理工大学 | A kind of cellulose base responsive to temperature type conductive hydrogel and its preparation method and application |
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