CN112430336B - Application of superfine bacterial cellulose powder in preparation of hydrogel - Google Patents
Application of superfine bacterial cellulose powder in preparation of hydrogel Download PDFInfo
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- CN112430336B CN112430336B CN202011296718.1A CN202011296718A CN112430336B CN 112430336 B CN112430336 B CN 112430336B CN 202011296718 A CN202011296718 A CN 202011296718A CN 112430336 B CN112430336 B CN 112430336B
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Abstract
The invention discloses a preparation method and application of bacterial cellulose ultrafine powder, and belongs to the field of preparation of bacterial cellulose powder. Aiming at the problems in the prior art, such as the adoption of a complex chemical treatment process, the increase of pollution or the influence on the structural properties of the material due to the temperature rise in the preparation process; and the preparation process is complicated and fussy, the universality is not strong and the like, the invention grinds the wet bacterial cellulose membrane to prepare the ultrafine particles by a simple low-temperature liquid nitrogen grinding method, the method is simple and easy to implement, the universality is strong, and the nanoscale bacterial cellulose ultrafine powder with good dispersion effect can be obtained. The bacterial cellulose ultrafine particles prepared by the method can be used as a reinforcing material and added into a polyglutamic acid hydrogel system to prepare the composite hydrogel, and compared with pure polyglutamic acid hydrogel, the thermal performance and the mechanical performance of the composite hydrogel are increased, so that a wider application space is provided for the composite hydrogel.
Description
The present application is a divisional application of the following applications: the application number is 201810580727.X, the invention name is a preparation method and application of ultrafine bacterial cellulose powder, and the application date is 2018-6-7.
Technical Field
The invention belongs to the field of preparation of bacterial cellulose powder, and particularly relates to a preparation method and application of bacterial cellulose ultrafine powder.
Background
Bacterial Cellulose (BC) is a novel biomaterial formed by microbial fermentation, and has the same molecular structural unit as plant Cellulose, but has many unique properties. Compared with plant cellulose, the bacterial cellulose has no associated products such as lignin, pectin, hemicellulose and the like, has ultrahigh purity, high crystallinity (generally more than 80 percent, and can reach 95 percent at most, and 65 percent of the plant cellulose) and high polymerization degree ((DP value 2000-8000)), and has high hydrophilicity, high biocompatibility and good mechanical property, so the bacterial cellulose has wide application in many fields.
Bacterial cellulose and cellulose can be used as reinforcing materials, are superior to plant cellulose in the aspects of purity, tensile strength, Young modulus and other physical and chemical properties, can be directly degraded in nature due to high biocompatibility, are commonly used in the fields of food, medicine and materials as fillers and are commonly used in the form of powder. The following methods have been reported for the preparation of cellulose powder:
the invention of publication No. CN110464, entitled "dissolving method for preparing nano-grade microcrystalline cellulose powder", provides a method for preparing cellulose powder with average size of 2.5-20nm by treating cotton and fibrilia by chemical treatment, washing, drying and crushing. The invention of publication No. CN1386775A, an ultrafine coconut microcrystalline cellulose powder and a preparation method thereof, discloses ultrafine cellulose particles with an average particle size of less than 20 microns obtained by compressing, dehydrating, drying, coarse crushing and ultrafine crushing coconut. The invention of publication No. CN1470552A, entitled "method for producing nano-sized cellulose particles", discloses a method for producing nano-sized cellulose particles by dissolution, comprising the steps of dissolving cellulose in a solvent, stirring to obtain a cellulose suspension, adding a precipitating solvent containing a dispersing agent to the suspension, stirring and emulsifying to obtain an emulsion containing nano-sized cellulose particles, wherein the average particle size of the particles is 50 to 200 nm. The invention of publication No. CN101935407A, entitled "method for preparing ultrafine bacterial cellulose powder", discloses an ultrafine bacterial cellulose powder obtained by repeatedly homogenizing and filtering bacterial cellulose with a homogenizer and finally spray-drying. The invention of publication No. CN104558639A, an invention of regenerated cellulose nano-particles and a preparation method thereof, thermally gelatinizes a cellulose solution to prepare hydrogel fibers, disperses the hydrogel fibers with a polyethylene oxide (PEO) aqueous solution, and combines strong shearing and mixing effects to finally obtain well-dispersed cellulose nano-particles.
Some of the above processes for preparing cellulose particles require complex chemical treatment of cellulose, and the preparation process is complex and tedious and has low universality; some simple physical grinding needs to be repeatedly ground and filtered, a certain amount of heat is generated in the traditional metal mechanical grinding process, even if cell disruption is not carried out at a very low temperature, temperature rise is difficult to avoid, and the structural property of an organic material matrix can be changed, so the methods for preparing the cellulose particles have certain defects.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of bacterial cellulose ultrafine powder and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
(1) preparing raw materials: purifying the bacterial cellulose wet film, and cutting into blocks;
(2) pre-cooling a grinding container: introducing liquid nitrogen (-196 deg.C) into the grinding tank of the mixing ball mill, and pre-freezing for 0.5-5 min;
(3) crushing raw materials: and adding the bacterial cellulose block into a grinding tank of a pre-cooled mixing ball mill, wherein the sample loading amount is 5-20g, the grinding time is 3-10min, and the grinding frequency is 10-28Hz, so as to obtain the bacterial cellulose ultrafine powder.
Preferably, in the step (1), the particle size of the BC block is 0.2-0.5cm × 0.2-0.5cm × 0.2-0.5 cm.
Preferably, in the step (3), the grinding tank has a volume of 50 ml.
The average particle size of the bacterial cellulose particles prepared by the method is 100-400 nm.
Another object of the present invention is to provide the above bacterial cellulose ultrafine powder.
The invention also aims to provide the application of the bacterial cellulose ultrafine powder in preparing hydrogel, and the specific technical scheme is as follows:
adding the bacterial cellulose ultrafine powder and a cross-linking agent into a polyglutamic acid aqueous solution with the mass concentration of 10-20wt%, adjusting the pH of the mixed solution to 4.0-4.5, and carrying out cross-linking reaction for 20-24h in a constant-temperature water bath at 40-60 ℃ in a mixed solution in which the mass ratio of the polyglutamic acid to the cross-linking agent to the bacterial cellulose is 10:2:1-10:6:7 to obtain the composite hydrogel.
Preferably, the crosslinking agent is one of ethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether.
Advantageous effects
(1) A simple method for preparing ultrafine bacterial cellulose particles is provided for a wet BC film by using a freezing mixing ball mill. The wet BC membrane is lack of brittleness, the BC can be embrittled by introducing low-temperature liquid nitrogen, the grinding is convenient, and meanwhile, a sample can be always in the liquid nitrogen at the temperature of-196 ℃ in the grinding process, so that the sample is guaranteed to be never denatured.
(3) Simple operation, high speed, high efficiency and no pollution.
(3) Can be applied to the preparation of various cellulose ultrafine particles and has strong universality.
(4) The bacterial cellulose ultrafine particles prepared by the method can be used as a reinforcing material and added into a polyglutamic acid hydrogel system to prepare composite hydrogel, compared with a single network of pure polyglutamic acid hydrogel, the bacterial cellulose ultrafine particles in a specific nanometer level range prepared by the method are added, the prepared composite hydrogel forms a semi-interpenetrating network structure, and meanwhile, the added ultrafine particles have larger specific surface area compared with conventional fillers, so that the thermal property and the mechanical property of the finally obtained composite hydrogel are remarkably improved, and a wider application space is provided for the composite hydrogel.
Drawings
FIG. 1 is a graph showing the particle size of ultrafine cellulose particles obtained in example 1;
FIG. 2 is a graph showing the particle size of the ultrafine cellulose particles obtained in example 2;
FIGS. 3 and 4 are the results of the mechanical property tests comparing the composite hydrogel (γ -PGA/BC) with the polyglutamic acid hydrogel (γ -PGA) in example 5.
Detailed Description
Example 1:
weighing about 5g of bacterial cellulose membrane, cutting the membrane into uniform small fragments (0.3 multiplied by 0.3cm) by using scissors, adding the fragments into a 50ml ball milling tank of a ball mill, introducing liquid nitrogen for pre-freezing for 0.5min, grinding for 3min at the grinding frequency of 28Hz, and obtaining the bacterial cellulose ultrafine powder with the average particle size of 150nm by adopting the method. FIG. 1 is a particle size chart of the bacterial cellulose powder of example 1.
Example 2:
weighing about 7g of bacterial cellulose membrane, cutting the membrane into uniform small fragments (0.3 multiplied by 0.3cm) by using scissors, adding the fragments into a 50ml ball milling tank of a ball mill, introducing liquid nitrogen for pre-freezing for 4min, grinding for 5min at the grinding frequency of 10Hz, and obtaining the bacterial cellulose ultrafine powder with the average particle size of 400nm by adopting the method. FIG. 2 is a particle size chart of the bacterial cellulose powder of example 2.
Example 3:
weighing about 10g of bacterial cellulose membrane, cutting the membrane into uniform small fragments (0.3 multiplied by 0.3cm) by using scissors, adding the fragments into a 50ml ball milling tank of a ball mill, introducing liquid nitrogen for pre-freezing for 5min, grinding for 10min at the grinding frequency of 28Hz, and obtaining the bacterial cellulose ultrafine powder with the average particle size of 200nm by adopting the method.
Example 4:
weighing about 10g of bacterial cellulose membrane, cutting the membrane into uniform small fragments (0.4 multiplied by 0.4cm) by using scissors, adding the fragments into a 50ml ball milling tank of a ball mill, introducing liquid nitrogen for pre-freezing for 5min, grinding for 8min at the grinding frequency of 28Hz, and obtaining the bacterial cellulose ultrafine powder with the average particle size of 270nm by adopting the method.
Example 5:
adding a crosslinking agent ethylene glycol diglycidyl ether and bacterial cellulose ultrafine powder prepared by the method shown in example 1 into a polyglutamic acid (gamma-PGA) aqueous solution with the mass concentration of 12 wt.% and mixing (the aqueous solution solvent is deionized water), wherein in the mixed solution, the ratio of polyglutamic acid: a crosslinking agent: the mass ratio of the bacterial cellulose is 10:4:1(w/w), the pH value of the solution is adjusted to be 4.0, and the crosslinking reaction is carried out for 20 hours in a thermostatic water bath at 50 ℃ to obtain the composite hydrogel.
Comparing the mechanical properties of the composite hydrogel and the polyglutamic acid hydrogel, it can be seen from fig. 3 and 4 that the tensile strength and the compressive strength of the composite hydrogel (γ -PGA/BC) added with the bacterial cellulose particles are respectively increased from 14.64kPa and 277kPa to 23.4kPa and 473.5kPa higher than those of the pure polyglutamic acid hydrogel (γ -PGA), and are respectively increased by about 60% and 70% higher than those of the pure polyglutamic acid hydrogel (γ -PGA), and compared with the similar experiments, delisha et al, in the irradiation preparation and properties of the bacterial cellulose/polyglutamic acid composite hydrogel, utilize bacterial cellulose to reinforce polyglutamic acid, and obtain the maximum compressive strength of 314kPa, while the compressive strength of the cellulose particle reinforced polyglutamic acid hydrogel obtained in this example is 473kPa, which indicates that the cellulose ultrafine particles have an obvious effect on the strength of the polyglutamic acid hydrogel, has certain potential for enhancing the strength of other high polymers.
It should be noted that the bacterial cellulose powders prepared in examples 2-4 of the present invention also have the above-mentioned experimental effects, and the differences between the examples are not significant.
Example 6
Adding a crosslinking agent polyethylene glycol diglycidyl ether and bacterial cellulose ultrafine powder prepared by the method shown in example 2 into a 10 wt.% aqueous solution of polyglutamic acid (γ -PGA) and mixing (the aqueous solution solvent is deionized water), wherein in the mixed solution, the weight ratio of polyglutamic acid: a crosslinking agent: the mass ratio of the bacterial cellulose is 10:5:1(w/w), the pH value of the solution is adjusted to be 4.0, and the crosslinking reaction is carried out for 20 hours in a thermostatic water bath at 50 ℃ to obtain the composite hydrogel.
Comparing the mechanical properties of the composite hydrogel and the polyglutamic acid hydrogel, the tensile strength and the compressive strength of the composite hydrogel respectively reach 280kPa and 490kPa, and the effect is similar to that of example 5. The tensile strength and the compressive strength of the composite hydrogel (gamma-PGA/BC) are obviously improved compared with those of pure polyglutamic acid hydrogel (gamma-PGA), and the cellulose ultrafine particles have obvious effect on improving the strength of the polyglutamic acid hydrogel and have great potential for enhancing the strength of other high polymers.
Claims (2)
1. An application of bacterial cellulose ultrafine powder in preparing hydrogel is characterized in that,
the method comprises the following steps: adding the bacterial cellulose ultrafine powder and a cross-linking agent into a polyglutamic acid aqueous solution with the mass concentration of 10-20wt%, adjusting the pH of the mixed solution to 4.0-4.5, and carrying out cross-linking reaction in a constant-temperature water bath at 40-60 ℃ for 20-24h to obtain a composite hydrogel, wherein the mass ratio of the polyglutamic acid to the cross-linking agent to the bacterial cellulose ultrafine powder is 10:2:1-10:6: 7;
the cross-linking agent is one of ethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether;
the preparation method of the bacterial cellulose ultrafine powder comprises the following steps:
(1) preparing raw materials: purifying the bacterial cellulose wet film, and cutting into blocks;
(2) pre-cooling a grinding container: introducing liquid nitrogen into a grinding tank of the mixing ball mill, and pre-freezing for 0.5-5 min;
(3) crushing raw materials: and adding the bacterial cellulose block into a grinding tank of a pre-cooled mixing ball mill, wherein the sample loading amount is 5-20g, the grinding time is 3-10min, and the grinding frequency is 10-28Hz, so as to obtain the bacterial cellulose ultrafine powder.
2. Use according to claim 1,
in the steps (2) and (3), the volume of the grinding tank is 50 ml.
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| CN201810580727.XA CN108948383B (en) | 2018-06-07 | 2018-06-07 | Preparation method and application of superfine bacterial cellulose powder |
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