CN112029124A - Micro/nano cellulose fiber/polyglycolic acid film and preparation method and application thereof - Google Patents
Micro/nano cellulose fiber/polyglycolic acid film and preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
The invention discloses a micro/nano cellulose cellosilk/polyglycolic acid film and a preparation method and application thereof. The method comprises the following steps: the method comprises the following steps: soaking cellulose raw materials in water to prepare suspension, and crushing ultrafine particles of the suspension to obtain micro/nano cellulose fibers to prepare dispersion liquid; and uniformly mixing the dispersion liquid and the polyglycolic acid solution, and drying to obtain the micro/nano cellulose silk/polyglycolic acid film. The invention prepares the micro/nano cellulose fiber by a simple mechanical method, does not use chemical drugs such as acid or alkali, and the like, and prepares the micro/nano cellulose fiber/polyglycolic acid composite film by mixing with polyglycolic acid solution. The film is applied to the field of packaging substrate enhancement and agriculture, can reduce and eliminate white pollution, and has wide social benefit and economic value.
Description
Technical Field
The invention belongs to the field of degradable films, and particularly relates to a micro/nano cellulose cellosilk/polyglycolic acid film and a preparation method and application thereof.
Background
Petroleum-based thin film products have excellent physical properties and are widely used in life and industrial production. However, the non-degradable property of petroleum-based film materials causes a great deal of environmental pollution, and the non-renewable raw materials also severely restrict the sustainable development of economy. With the progress of science and technology, the environmental protection and sustainable development are increasingly emphasized, and the demand of people on environment-friendly film materials is more and more urgent. Polyglycolic acid (PGA), which is a synthetic polymer material having good biodegradability and biocompatibility, is more and more important because it is gradually degraded after a certain time of use as a material, and finally becomes water and carbon dioxide, which are harmless to the human body, animals and plants, and natural environments, unlike conventional polymer materials having stable properties, such as plastics, rubbers, etc. However, it is relatively expensive and has low mechanical strength, which makes its application range greatly limited. The green and environment-friendly micro/nano cellulose fiber has the characteristics of degradability, rich sources, high mechanical strength and the like, and is popular with people in recent years. The use of micro/nanocellulose filamentation as a reinforcement material has been a hot spot for the development and utilization of micro/nanocellulose filamentation applications.
At present, a polyglycolic acid modified nanocrystalline cellulose composite material is prepared by performing melt polycondensation on nanocrystalline cellulose obtained by acidolysis and freeze drying of microcrystalline cellulose and glycolic acid under catalysis of stannic chloride dihydrate through microwave radiation (proceedings of the Jiaxing academy of academic, 2017,29(6), 52-55). However, the melt mixing preparation method has defects that more voids exist in the composite material, the mechanical properties of the material are reduced, and the use of the composite material is directly influenced. In addition, the acid method can seriously degrade the cellulose, cannot keep the amorphous region of the nano-cellulose, reduces the yield of the nano-cellulose, and cannot make the nano-cellulose form devillicate.
The micro/nano cellulose fiber prepared by the mechanical method has more devillicate fibrillation and higher yield of the micro/nano cellulose fiber. At present, no report is available about the preparation of the mechanically modified micro/nano cellulose fiber/polyglycolic acid composite film. Therefore, the micro/nano cellulose fibrils are prepared by utilizing natural renewable cellulose with rich resources through a simple and feasible mechanical method, and are compounded with polyglycolic acid to prepare the high-strength degradable film, so that the high-strength degradable film has wide market prospect, considerable economic value and good environmental benefit.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a micro/nano cellulose silk/polyglycolic acid film and a preparation method and application thereof.
The invention aims to make up for the defects of the prior art and provide a preparation method of a micro/nano cellulose cellosilk/polyglycolic acid composite film, which is simple and easy to implement and has good performance.
The invention also aims to provide application of the plant micro/nano cellulose fiber/polyglycolic acid film.
The purpose of the invention is realized by at least one of the following technical solutions.
The preparation method of the micro/nano cellulose fiber/polyglycolic acid film provided by the invention comprises the following steps:
(1) soaking a cellulose raw material in water, and then preparing the cellulose raw material into a suspension by using the water to obtain a cellulose suspension (plant or bacterial cellulose pulp suspension);
(2) carrying out ultrafine particle crushing treatment on the cellulose suspension in the step (1) by using an ultrafine particle crusher to obtain micro/nano cellulose fibers of a water dispersion system, centrifugally removing water (removing part of water to obtain high-concentration micro/nano cellulose fibers) to obtain micro/nano cellulose fibers, and preparing the micro/nano cellulose fibers into a micro/nano cellulose fiber water dispersion;
(3) uniformly mixing polyglycolic acid and a solvent to prepare a polyglycolic acid solution; and (3) uniformly mixing the micro/nano cellulose fiber aqueous dispersion liquid obtained in the step (2) with a polyglycolic acid solution, pouring the mixture into a film casting container, and drying the mixture (drying can be carried out at different temperatures) to obtain the degradable micro/nano cellulose fiber/polyglycolic acid film.
Further, the cellulose raw material in the step (1) is more than one of bacterial cellulose, cotton pulp, hemp pulp, hardwood pulp, softwood pulp and the like; the time for soaking the cellulose raw material in water is 12-48 h. The cellulose raw material is paper pulp and bacterial cellulose from different plant fiber sources.
Further, the mass percentage concentration of the cellulose suspension in the step (1) is 0.1-8%.
Preferably, the water in step (1) is distilled water.
Further, the conditions for the ultrafine particle pulverization treatment in step (2) are as follows: the gap of the superfine particle pulverizer is-20 to 100 mu m, the rotation speed of the superfine particle pulverizing treatment is 1500 to 6000r/min, and the cycle of the superfine particle pulverizing treatment is 10 to 30 times.
Preferably, the grinding disc gap of the superfine grain grinder in the step (2) is-10 microns, the rotating speed is 3000r/min, and the cycle period is 10 times.
Further, the mass percentage concentration of the micro/nano cellulose fiber aqueous dispersion in the step (2) is 1-15%.
Further, the solvent of the polyglycolic acid solution in the step (3) is one or more of water, methanol, ethanol, tetrahydrofuran, acetonitrile, acetone and n.n-dimethylformamide; the polymerization degree of the polyglycolic acid is 170-8000.
Preferably, the solvent of the polyglycolic acid solution of step (3) is a polar solution; the solvent of the polyglycolic acid solution is ethanol.
In step (3), the polyglycolic acid is used in an amount of 1 to 99% by dry weight based on the weight of the film.
Further, the mass of the polyglycolic acid in the step (3) is 1 to 1000% of the mass of the cellulose in the step (1).
Further, the drying temperature in the step (3) is 25-110 ℃, and the drying time is 1-24 h.
Preferably, the temperature of the drying treatment in the step (3) is 25-80 ℃.
The invention provides a micro/nano cellulose fiber/polyglycolic acid film prepared by the preparation method.
The micro/nano cellulose cellosilk/polyglycolic acid film provided by the invention can be applied to packaging products, the agricultural field or matrix protection.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method provided by the invention, the composite membrane is prepared by preparing the high devillicate broomed micro/nano cellulose fibers by a mechanical method and mixing the micro/nano cellulose fibers with the polyglycolic acid, so that the manufacturing process of the nano cellulose fiber/polyglycolic acid composite membrane is improved, and the effects of simplifying the process and facilitating the operation are achieved.
(2) The preparation method provided by the invention has the advantages that the used micro/nano cellulose fiber has rich surface hydroxyl and higher surface energy, so that the micro/nano cellulose fiber can be compatible with polyglycolic acid, and good combination can be formed through better van der Waals force action, hydrogen bond action and interface fusion action, so that multiple ways and methods are provided for the application of the micro/nano cellulose fiber, and the application range of the cellulose fiber is expanded.
(3) According to the preparation method provided by the invention, the biodegradable base material is adopted, and the prepared micro/nano cellulose silk/polyglycolic acid film is degradable and cannot generate harmful influence on the environment; the prepared micro/nano cellulose fiber/polyglycolic acid film has good mechanical strength and transparency (for example, the tensile strength is 60-120 MPa, and the light transmittance is more than 90 percent), and can be applied to the fields of packaging, agriculture or matrix protection.
Drawings
Fig. 1 is a flow chart of a manufacturing process of a micro/nanocellulose filament/polyglycolic acid film.
Fig. 2 is a surface SEM image of the micro/nanocellulose filament/polyglycolic acid film in example 3 of the present invention.
Fig. 3 is a surface SEM image of the micro/nanocellulose filament/polyglycolic acid film in example 4 of the present invention.
Fig. 4 is a cross-sectional SEM image of the micro/nanocellulose filament/polyglycolic acid film in example 4 of the present invention.
Fig. 5 is a graph showing the results of light reflectance and light transmittance of the micro/nanocellulose filament/polyglycolic acid film in example 6 of the present invention.
FIG. 6 is a graph showing the degradation pathway of cellulose and polyglycolic acid according to the present invention.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. In the preparation method, the raw material cellulose and other reagents can be purchased from the market and can be directly used after being obtained.
The preparation method of the micro/nano cellulose filament/polyglycolic acid film of the present invention is performed with reference to the flow chart of the preparation process of the micro/nano cellulose filament/polyglycolic acid film of fig. 1.
Example 1
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 50g of dry weight of bacterial cellulose is soaked in water for 12 hours and then prepared into a pulp suspension with the mass percentage concentration of 1%.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 1% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotation speed of 1500r/min and the clearance of-20 μm, performing circulating grinding treatment for 10 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 15%.
(3) Polyglycolic acid (with a polymerization degree of 170) is prepared into a polyglycolic acid water solution with a mass fraction of 30%.
(4) And (3) uniformly mixing 20g of the micro/nano cellulose silk aqueous dispersion prepared in the step (2) and 10g of the polyglycolic acid aqueous solution prepared in the step (3), pouring the mixture into a film casting container, and drying the mixture at 80 ℃ for 24 hours to prepare the micro/nano cellulose silk/polyglycolic acid film (the tensile modulus is 80.1MPa, and the elongation at break is 10.3%).
Example 2
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) hardwood pulp with the dry weight of 200g is placed in water for soaking for 48 hours and then prepared into pulp suspension with the mass percentage concentration of 8%.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 8% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotating speed of 3000r/min and the gap of-10 μm, performing circulating grinding treatment for 30 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 10%.
(3) Polyglycolic acid (polymerization degree of 1000) is prepared into polyglycolic acid ethanol solution with mass fraction of 20%.
(4) And (3) uniformly mixing 10g of the micro/nano cellulose silk water dispersion prepared in the step (2) and 495g of the polyglycolic acid ethanol solution prepared in the step (3), pouring the mixture into a film casting container, and drying the mixture at 25 ℃ for 6 hours to prepare the micro/nano cellulose silk/polyglycolic acid film (the tensile modulus is 63.8MPa, and the elongation at break is 15.9%).
Example 3
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 200g of softwood pulp in dry weight is soaked in water for 48 hours and then prepared into pulp suspension with the mass percentage concentration of 4%.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 4% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotating speed of 3000r/min and the gap of-10 μm, performing circulating grinding treatment for 20 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 15%.
(3) Polyglycolic acid (with a polymerization degree of 2100) was taken to prepare a polyglycolic acid methanol solution with a mass fraction of 20%.
(4) 100g of the aqueous dispersion of the micro/nano cellulose filaments prepared in the step (2) and 25g of the polyglycolic acid methanol solution prepared in the step (3) were uniformly mixed and poured into a film casting container, and then dried at 35 ℃ for 6 hours to prepare a micro/nano cellulose filaments/polyglycolic acid film (tensile modulus of 89.51MPa, elongation at break of 7.9%).
From the front SEM image in fig. 2, it can be seen that the prepared micro/nanocellulose filament/polyglycolic acid thin film had a flat surface without voids, which indicates that the bonding between the micro/nanocellulose filament and polyglycolic acid was good.
Example 4
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 200g of dry hemp pulp is soaked in water for 48 hours and then prepared into a pulp suspension with the mass percentage concentration of 1 percent.
(2) 2.5L of the pulp suspension obtained in step (1) was pulverized with an ultrafine pulverizer (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at 6000r/min and a gap of-30 μm for 30 cycles to obtain a 1% w/w aqueous dispersion of micro/nanocellulose filaments.
(3) Polyglycolic acid (with a polymerization degree of 3800) is prepared into a polyglycolic acid tetrahydrofuran solution with a mass fraction of 1%.
(4) And (3) uniformly mixing 500g of the micro/nano cellulose silk aqueous dispersion prepared in the step (2) and 1000g of the polyglycolic acid tetrahydrofuran solution prepared in the step (3), pouring the mixture into a film casting container, and drying the mixture at 65 ℃ for 24 hours to prepare the micro/nano cellulose silk/polyglycolic acid film (the tensile modulus is 72.34MPa, and the elongation at break is 12.5%).
From the surface and cross-sectional SEM images in fig. 3 and 4, it can be seen that the prepared micro/nanocellulose filaments are uniformly dispersed in the micro/nanocellulose filament/polyglycolic acid thin film, and the alignment of the micro/nanocellulose filaments can be clearly seen under the shearing force without a significant phase separation phenomenon, which indicates that the micro/nanocellulose filaments have good compatibility with polyglycolic acid.
Example 5
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 200g of cotton pulp with dry weight is soaked in water for 48 hours and then prepared into pulp suspension with the mass percentage concentration of 2 percent.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 1% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotating speed of 3000r/min and the gap of-15 μm, performing circulating grinding treatment for 10 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 10%.
(3) Polyglycolic acid (polymerization degree of 4500) is prepared into polyglycolic acid N.N-dimethylformamide solution with mass fraction of 1%.
(4) 100g of the aqueous dispersion of the micro/nanocellulose filaments prepared in the step (2) and 10g of the polyglycolic acid N.N-dimethylformamide solution prepared in the step (3) were uniformly mixed and poured into a casting container, and then dried at 80 ℃ for 24 hours to prepare a micro/nanocellulose filaments/polyglycolic acid film (tensile modulus of 118.83MPa, elongation at break of 4.8%).
Example 6
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 200g of softwood pulp with a dry weight is placed in water for soaking for 48 hours, and then pulp suspension with the mass percentage concentration of 2% is prepared.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 1% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotating speed of 6000r/min and the clearance of-15 μm, performing circulating grinding treatment for 10 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 5%.
(3) Polyglycolic acid (polymerization degree of 6200) is prepared into a polyglycolic acid acetone solution with the mass fraction of 1%.
(4) And (3) uniformly mixing 100g of the micro/nano cellulose silk aqueous dispersion prepared in the step (2) and 100g of the polyglycolic acid acetone solution prepared in the step (3), pouring the mixture into a film casting container, and drying the mixture at 30 ℃ for 24 hours to prepare the micro/nano cellulose silk/polyglycolic acid film (the tensile modulus is 92.6MPa, and the elongation at break is 5.8%).
Fig. 5 shows the reflection rate and light transmittance data of the micro/nano cellulose fiber/polyglycolic acid film, and it can be seen that the film has a reflection rate of less than 10% in the visible light region and a light transmittance of more than 90%, indicating that the film has good optical properties.
Example 7
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 200g of softwood pulp with a dry weight is placed in water for soaking for 48 hours, and then pulp suspension with the mass percentage concentration of 2% is prepared.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 1 percent obtained in the step (1), crushing by using an ultrafine particle crusher (model: MKCA6-2J, Japan ZengHai Industrial Co., Ltd.), circularly crushing for 2 times at the rotating speed of 2000r/min and the clearance of 100 mu m, circularly crushing for 5 times at the rotating speed of 3000r/min and the clearance of 10 mu m, and circularly crushing for 10 times at the rotating speed of 6000r/min and the clearance of-15 mu m to obtain the micro/nano cellulose fibers of the water dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber water dispersion with the mass fraction of 2 percent.
(3) Polyglycolic acid (polymerization degree of 7000) was taken to prepare a polyglycolic acid acetonitrile solution with a mass fraction of 1%.
(4) And (3) uniformly mixing 80g of the micro/nano cellulose silk aqueous dispersion prepared in the step (2) and 200g of the polyglycolic acid acetonitrile solution prepared in the step (3), pouring the mixture into a film casting container, and drying the mixture at 40 ℃ for 12 hours to prepare the micro/nano cellulose silk/polyglycolic acid film (the tensile modulus is 78.23MPa, and the elongation at break is 11.2%).
Example 8
A preparation method of a micro/nano cellulose fiber/polyglycolic acid film comprises the following steps:
(1) 200g of softwood pulp with a dry weight is placed in water for soaking for 48 hours, and then pulp suspension with the mass percentage concentration of 2% is prepared.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 1% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotating speed of 6000r/min and the clearance of-15 μm, performing circulating grinding treatment for 10 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 4%.
(3) Polyglycolic acid (with a polymerization degree of 8000) is prepared into a mixed solution of polyglycolic acid acetone and tetrahydrofuran with a mass fraction of 2%, and the mass fraction of acetone in the mixed solution is 50%.
(4) And (3) uniformly mixing 100g of the micro/nano cellulose fibril aqueous dispersion prepared in the step (2) and 75g of the polyglycolic acid acetone and tetrahydrofuran mixed solution prepared in the step (3), pouring the mixture into a film casting container, and drying the mixture at 40 ℃ for 16 hours to prepare the micro/nano cellulose fibril/polyglycolic acid film (the tensile modulus is 88.3MPa, and the elongation at break is 8.7%).
Comparative example 1
A preparation method of a micro/nano cellulose fiber film comprises the following steps:
(1) 200g of softwood pulp with a dry weight is placed in water for soaking for 48 hours, and then pulp suspension with the mass percentage concentration of 2% is prepared.
(2) Taking 2.5L of the pulp suspension with the mass fraction of 1% obtained in the step (1), performing grinding treatment by using an ultrafine particle grinder (model: MKCA6-2J, Japan ZengHai industries, Ltd.) at the rotating speed of 6000r/min and the clearance of-15 μm, performing circulating grinding treatment for 10 times to obtain micro/nano cellulose fibers of an aqueous dispersion system, and then removing part of water by centrifugation to prepare the micro/nano cellulose fiber aqueous dispersion with the mass fraction of 5%.
(3) And (3) pouring 100g of the aqueous dispersion of the micro/nano cellulose fibers prepared in the step (2) into a film casting container, and drying at 50 ℃ for 24h to prepare the micro/nano cellulose fiber film.
Comparative example 2
A polyglycolic acid film is prepared by the following steps:
(1) 10g of polyglycolic acid (polymerization degree of 1000) is prepared into an ethanol solution with the mass fraction of 5%.
(2) Pouring 100g of the polyglycolic acid ethanol solution prepared in the step (1) into a casting container, and drying at 25 ℃ for 12h to prepare the polyglycolic acid film.
Effects of the embodiment
In examples 1 to 8 and comparative examples 1 to 2, micro/nanocellulose filament/polyglycolic acid films were prepared in various content ratios and measured for strength and elongation at break in accordance with GB/T1040-2006 using 100N sensors in a testing machine with a pitch of 30mm and a drawing rate of 10mm/min, and the results are shown in Table 1.
TABLE 1
As can be seen from the application test results in table 1, the addition of the micro/nanocellulose filaments can increase the tensile strength of the polyglycolic acid film and reduce the elongation at break thereof.
In the preparation method provided by the invention, the prepared micro/nano cellulose silk/polyglycolic acid film can be degraded by adopting a biodegradable base material (a degradation path diagram of cellulose and polyglycolic acid can be shown in figure 6), and has no harmful effect on the environment.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a micro/nano cellulose fiber/polyglycolic acid film is characterized by comprising the following steps:
(1) soaking a cellulose raw material in water, and preparing into a suspension to obtain a cellulose suspension;
(2) carrying out ultramicro particle crushing treatment on the cellulose suspension liquid obtained in the step (1) to obtain micro/nano cellulose fibers of a water dispersion system, centrifuging to remove water to obtain micro/nano cellulose fibers, and preparing the micro/nano cellulose fibers into micro/nano cellulose fiber water dispersion liquid;
(3) uniformly mixing polyglycolic acid and a solvent to prepare a polyglycolic acid solution; and (3) uniformly mixing the micro/nano cellulose fiber aqueous dispersion liquid obtained in the step (2) with a polyglycolic acid solution, pouring the mixture into a film casting container, and drying to obtain the micro/nano cellulose fiber/polyglycolic acid film.
2. The method for preparing a micro/nanocellulose filament/polyglycolic acid film according to claim 1, wherein the cellulose raw material in step (1) is one or more of bacterial cellulose, cotton pulp, hemp pulp, hardwood pulp, and softwood pulp; the time for soaking the cellulose raw material in water is 12-48 h.
3. The method for preparing a micro/nanocellulose filament/polyglycolic acid membrane according to claim 1, wherein the cellulose suspension of step (1) has a mass percentage concentration of 0.1% to 8%.
4. The method for producing a micro/nanocellulose filament/polyglycolic acid film according to claim 1, wherein the conditions for the ultrafine particle pulverization treatment in step (2) are: the gap of the superfine particle pulverizer is-20 μm-100 μm, the rotation speed of superfine particle pulverizing treatment is 1500r/min-6000r/min, and the cycle of superfine particle pulverizing treatment is 10-30 times.
5. The method for producing a micro/nanocellulose filament/polyglycolic acid film according to claim 1, wherein the concentration of the aqueous dispersion of micro/nanocellulose filaments in step (2) is 1 to 15% by mass.
6. The method for preparing a micro/nanocellulose filament/polyglycolic acid film according to claim 1, wherein the solvent of the polyglycolic acid solution of step (3) is one or more of water, methanol, ethanol, tetrahydrofuran, acetonitrile, acetone, and n.n-dimethylformamide; the polymerization degree of the polyglycolic acid is 170-8000.
7. The method for producing a micro/nanocellulose filament/polyglycolic acid film according to claim 1, wherein in step (3), polyglycolic acid is used in an amount of 1 to 99% by dry weight based on the mass of the micro/nanocellulose filament/polyglycolic acid film.
8. The method for preparing a micro/nanocellulose filament/polyglycolic acid film according to claim 1, wherein the temperature of the drying treatment in step (3) is 25 to 110 ℃, and the time of the drying treatment is 1 to 24 hours.
9. A micro/nanocellulose filament/polyglycolic acid film obtained by the production method according to any one of claims 1 to 8.
10. Use of the micro/nanocellulose filament/polyglycolic acid film of claim 9 in packaging products, agriculture or matrix protection.
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| CN113337013A (en) * | 2021-06-03 | 2021-09-03 | 华南理工大学 | Cellulose nanofibril-PBAT composite film and preparation method and application thereof |
| CN115418092A (en) * | 2022-10-11 | 2022-12-02 | 道恩周氏(青岛)复合包装材料有限公司 | Polyglycolic acid material and preparation method and application thereof |
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