CN106750558B - Degradable antibacterial film based on rice hulls and preparation method thereof - Google Patents
Degradable antibacterial film based on rice hulls and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- 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
- C08J2301/08—Cellulose derivatives
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- C08J2301/28—Alkyl ethers
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The invention relates to a degradable antibacterial film based on rice hulls and a preparation method thereof, the degradable antibacterial film based on the rice hulls is prepared by 4-9% of rice hull powder, 15-18% of sodium hydroxide, 6-8% of xanthan gum, 1.0-2.5% of chitosan, 8.0-10.0% of citric acid, 11.0-15.0% of lactic acid, 3-5% of carrageenan, 20-25% of sodium carboxymethyl cellulose, 4-5% of allyl isothiocyanate, 13-15% of glycerol and 10-15% of deionized water according to the mass-volume ratio, wherein the rice hull powder is 270-mesh rice hull powder; the degradable antibacterial film based on the rice hulls has the advantages of 80-230 mu m of film thickness, 56.7-74.6 MP of tensile strength, 21.7-37.9 percent of elongation at break and 17-28 times of folding endurance. The fine rice hull powder particles and the antibacterial substance are uniformly distributed in the film material, and the prepared packaging film has strong mechanical property and barrier property and can realize heat sealing.
Description
One, the technical field
The invention relates to the technical field of packaging films, in particular to a degradable antibacterial film based on rice hulls and a preparation method thereof.
Second, background Art
The packaging film is widely applied, but because the packaging film is generally not degradable, the packaging film is usually not applied for the second time after being disassembled from a package, but is discarded to form non-degradable garbage, thereby polluting the environment.
The annual output of rice in the black Longjiang reclamation area reaches about 210 million jin, and the rice hulls are 20% of the processing amount of the rice, so that the rice hull emission in the reclamation area reaches 42 million jin, and the rice hull yield is quite rich. The degradable antibacterial film prepared by using rice husks as a matrix material has no literature and patent report.
Third, the invention
The invention aims to provide a degradable antibacterial film based on rice hulls, which is used for solving the problems of environmental pollution caused by difficult degradation of plastic packaging films and composite packaging films in the prior art and improving the additional value of the rice hulls, and also aims to provide a preparation method of the degradable antibacterial film based on the rice hulls.
In order to achieve the purpose, the invention adopts the following specific technical scheme: the degradable antibacterial film based on the rice hulls is prepared from 4-8% of rice hull powder, 15-18% of sodium hydroxide, 6-8% of xanthan gum, 1.0-2.5% of chitosan, 8.0-10.0% of citric acid, 11.0-15.0% of lactic acid, 3-5% of carrageenan, 20-25% of sodium carboxymethyl cellulose, 4-5% of allyl isothiocyanate, 13-15% of glycerol and 10-15% of deionized water according to the mass-volume ratio, wherein the rice hulls are 270-mesh rice hull powder; the degradable antibacterial film based on the rice hulls has the advantages of 74-120 mu m of thickness, 34.8-67.2 MP of tensile strength, 21.7-27.8 percent of elongation at break and 17-28 times of folding endurance.
The preparation method of the degradable antibacterial film based on the rice hulls comprises the following steps:
step one, selecting mildew-free rice hulls, and drying the rice hulls in an electrothermal blowing drying oven at 80-100 ℃ for 14-16 minutes;
step two, crushing the dried rice hulls into 270-mesh rice hull powder, and meanwhile, preparing according to the mass-volume ratio: 4-8% of rice hull powder, 15-18% of sodium hydroxide, 6-8% of xanthan gum, 1.0-2.5% of chitosan, 8.0-10.0% of citric acid, 11.0-15.0% of lactic acid, 3-5% of carrageenan, 20-25% of sodium carboxymethyl cellulose, 4-5% of allyl isothiocyanate, 13-15% of glycerol and 10-15% of deionized water;
step three, according to the mixture ratio in the step two: adding the rice hull powder into 15-18% sodium hydroxide solution, stirring for 16-20 minutes, adding 1.0-2.5% chitosan into a mixed solution of 8.0-10.0% citric acid and 11.0-15.0% lactic acid, stirring in a magnetic stirrer until the chitosan is completely dissolved, adding the mixture into the mixed solution of the rice hull powder and the sodium hydroxide, adding 6-8% xanthan gum, 3-5% carrageenan, 20-25% sodium carboxymethylcellulose and 13-15% glycerol, stirring in a water bath kettle at the temperature of 60-70 ℃ for 40-50 minutes until the mixture is uniform, adding 4-5% allyl isothiocyanate while stirring, and cooling;
homogenizing in a high-pressure homogenizer at 20-26 ℃ under 115-125 MPa under 3 circulation conditions;
and step five, casting the mixture on a PC board to form a film, horizontally placing the film in an electrothermal blowing drying oven for drying, wherein the drying time is 180-300 min, the temperature is 40-60 ℃, and then cooling to room temperature to remove the film from the PC board, so as to obtain the degradable antibacterial film based on the rice hulls.
Has the advantages that:
1. the invention takes rice hulls as main raw materials and various auxiliary agents as auxiliary materials to prepare the degradable antibacterial film of the rice hulls. The high-pressure homogenization technology is applied to the preparation process of the film, so that the fine particles of the rice hull powder and the antibacterial substance are uniformly distributed in the film material, the prepared packaging film has strong mechanical property and barrier property, and the film can be heated and sealed.
2. The raw materials used by the invention are all green packaging materials, do not cause pollution to the environment, and simultaneously have antibacterial property and degradability.
3. The method greatly improves the economic value and the added value of the rice hulls, has simple film preparation method and low cost, and is suitable for large-scale production.
Fourth, detailed description of the invention
The invention is further illustrated below:
example 1:
the degradable antibacterial film based on the rice hulls is prepared from 4% of rice hull powder, 15% of sodium hydroxide, 6% of xanthan gum, 1.5% of chitosan, 8.0% of citric acid, 11.0% of lactic acid, 3% of carrageenan, 20% of sodium carboxymethyl cellulose, 4% of allyl isothiocyanate, 13% of glycerol and 10% of deionized water according to the mass-volume ratio, wherein the rice hull powder is 270-mesh rice hull powder. The mass-volume ratio is the ratio of the mass of all components to the volume of a certain component, and the volume of all components is the total volume of the rice hull powder, the sodium hydroxide, the xanthan gum, the chitosan, the citric acid, the lactic acid, the carrageenan, the sodium carboxymethyl cellulose, the allyl isothiocyanate, the glycerol and the deionized water, and the following is the same if the mass-volume ratio of the rice hull powder is the ratio of the mass of the rice hull powder to the total volume.
The preparation method of the degradable antibacterial film based on the rice hulls comprises the following steps:
(1) selecting mildew-free rice hulls, and drying the rice hulls in an electrothermal blowing drying oven at 80 ℃ for 16 minutes;
(2) crushing the dried rice hulls into rice hull powder;
(3) adding 4% (w/v) rice hull powder into 15% (w/v) sodium hydroxide solution, stirring for 20 minutes, adding 1.5% (w/v) chitosan into a mixed solution of 8.0% (w/v) citric acid and 11.0% (w/v) lactic acid, stirring in a magnetic stirrer until the chitosan is completely dissolved, adding the mixture into the mixed solution of the rice hull powder and the sodium hydroxide, adding 6% (w/v) xanthan gum, 3.0% (w/v) carrageenan, 20% (w/v) sodium carboxymethyl cellulose, 13% (w/v) glycerol, stirring for 40 minutes in a water bath kettle at 60 ℃ until the mixture is uniform, adding 4% (w/v) allyl isothiocyanate while stirring, and cooling;
(4) homogenizing under high pressure at 20 deg.C under 115MPa for 3 cycles;
(5) casting the mixture on a PC board to form a film, horizontally placing the film in an electrothermal blowing dry box for drying (the time is 180min and the temperature is 60 ℃), and cooling the film to room temperature to remove the film from the PC board.
The obtained film has the thickness of 74 mu m, the tensile strength of 34.8MP, the elongation at break of 21.7 percent and the folding endurance of 28 times, has excellent degradability when the weight loss rate reaches about 80 percent in a soil burying degradation test after 90 days, and has heat sealability and good antibacterial property.
Example 2:
the degradable antibacterial film based on the rice hulls is prepared from 6% of rice hull powder, 17% of sodium hydroxide, 7% of xanthan gum, 2% of chitosan, 9% of citric acid, 13% of lactic acid, 4% of carrageenan, 22% of sodium carboxymethylcellulose, 4.5% of allyl isothiocyanate, 14% of glycerol and 12% of deionized water in percentage by mass and volume, wherein the rice hull powder is 270-mesh rice hull powder.
The preparation method of the degradable antibacterial film based on the rice hulls comprises the following steps:
(1) selecting mildew-free rice hulls, and drying the rice hulls in an electrothermal blowing drying oven at 90 ℃ for 15 minutes;
(2) crushing the dried rice hulls into rice hull powder;
(3) adding 6% (w/v) rice hull powder into 17% (w/v) sodium hydroxide solution, stirring for 18 minutes, adding 2% (w/v) chitosan into a mixed solution of 9.0% (w/v) citric acid and 13.0% (w/v) lactic acid, stirring in a magnetic stirrer until the chitosan is completely dissolved, adding the mixture into the mixed solution of the rice hull powder and the sodium hydroxide, adding 7% (w/v) xanthan gum, 4% (w/v) carrageenan, 22% (w/v) sodium carboxymethyl cellulose, 14% (w/v) glycerol, stirring for 50 minutes in a 65 ℃ water bath kettle until the mixture is uniform, adding 4.5% (w/v) allyl isothiocyanate while stirring, and cooling;
(4) homogenizing under high pressure at 23 deg.C under 120MPa for 3 cycles;
(5) casting the mixture on a PC board to form a film, horizontally placing the film in an electrothermal blowing dry box for drying (the time is 240min and the temperature is 50 ℃), and cooling the film to room temperature to remove the film from the PC board.
The obtained film has the thickness of 96 mu m, the tensile strength of 59.7MP, the elongation at break of 23.4 percent and the folding endurance of 24 times, has excellent degradability when the weight loss rate reaches about 80 percent in a soil burying degradation test after 90 days, and has heat sealability and good antibacterial property.
Example 3:
the degradable antibacterial film based on the rice hulls is prepared from 8% of rice hull powder, 18% of sodium hydroxide, 8% of xanthan gum, 2.5% of chitosan, 10.0% of citric acid, 15.0% of lactic acid, 5% of carrageenan, 25% of sodium carboxymethyl cellulose, 5% of allyl isothiocyanate, 15% of glycerol and 15% of deionized water in a mass-volume ratio, wherein the rice hull powder is 270-mesh rice hull powder.
The preparation method of the degradable antibacterial film based on the rice hulls comprises the following steps:
(1) selecting mildew-free rice hulls, and drying the rice hulls in an electrothermal blowing drying oven at 100 ℃ for 14 minutes;
(2) crushing the dried rice hulls into rice hull powder;
(3) adding 8% (w/v) rice hull powder into 18% (w/v) sodium hydroxide solution, stirring for 16 minutes, adding 2.5% (w/v) chitosan into a mixed solution of 10.0% (w/v) citric acid and 15.0% (w/v) lactic acid, stirring in a magnetic stirrer until the chitosan is completely dissolved, adding the mixture into the mixed solution of the rice hull powder and the sodium hydroxide, adding 8% (w/v) xanthan gum, 5% (w/v) carrageenan, 25% (w/v) sodium carboxymethyl cellulose, 15% (w/v) glycerol, stirring for 50 minutes in a 70 ℃ water bath kettle until the components are uniformly mixed, adding 5% (w/v) allyl isothiocyanate while stirring, and cooling;
(4) homogenizing under high pressure at 26 deg.C under 125MPa for 3 cycles;
(5) casting the mixture on a PC board to form a film, horizontally placing the film in an electrothermal blowing dry box for drying (the time is 300min, the temperature is 40 ℃), and cooling the film to room temperature to remove the film from the PC board.
The obtained film has the thickness of 120 mu m, the tensile strength of 67.2MP, the elongation at break of 27.8 percent and the folding endurance of 17 times, has excellent degradability when the weight loss rate reaches about 80 percent in a soil burying degradation test after 90 days, and has heat sealability and good antibacterial property.
The rice hull packaging film provided by the invention is free of pollution in the whole production and processing period, the comprehensive utilization of rice hulls reduces the pollution hazard of rice hull wastes to urban environment and atmosphere, and the rice hull packaging film belongs to a real green environment-friendly packaging material; after being discarded, the biodegradable plastic can be completely degraded in natural environment, and has no pollution and harm to the environment; the application proportion of the plastic packaging material is reduced, the effects of restraining and reducing white pollution are achieved, the consumption of non-renewable energy is reduced, a large amount of forest resources are saved, and the pollution hazard of industrial wastewater generated by papermaking to the environment is avoided.
Claims (1)
1. A degradable antibacterial film based on rice hulls is characterized in that: the degradable antibacterial film based on the rice hulls is prepared by 4-8% of rice hull powder, 15-18% of sodium hydroxide, 6-8% of xanthan gum, 1.0-2.5% of chitosan, 8.0-10.0% of citric acid, 11.0-15.0% of lactic acid, 3-5% of carrageenan, 20-25% of sodium carboxymethyl cellulose, 4-5% of allyl isothiocyanate, 13-15% of glycerol and 10-15% of deionized water according to the mass-volume ratio, wherein the rice hull powder is 270-mesh rice hull powder; the degradable antibacterial film based on the rice hulls has the thickness of 74-120 mu m, the tensile strength of 34.8-67.2 MP, the elongation at break of 21.7-27.8 percent and the folding endurance of 17-28 times;
the preparation method of the degradable antibacterial film based on the rice hulls comprises the following steps:
step one, selecting mildew-free rice hulls, and drying the rice hulls in an electrothermal blowing drying oven at 80-100 ℃ for 14-16 minutes;
step two, crushing the dried rice hulls into 270-mesh rice hull powder, and meanwhile, preparing according to the mass-volume ratio: 4-8% of rice hull powder, 15-18% of sodium hydroxide, 6-8% of xanthan gum, 1.0-2.5% of chitosan, 8.0-10.0% of citric acid, 11.0-15.0% of lactic acid, 3-5% of carrageenan, 20-25% of sodium carboxymethyl cellulose, 4-5% of allyl isothiocyanate, 13-15% of glycerol and 10-15% of deionized water;
step three, according to the mixture ratio in the step two: adding the rice hull powder into 15-18% sodium hydroxide solution, stirring for 16-20 minutes, adding 1.0-2.5% chitosan into a mixed solution of 8.0-10.0% citric acid and 11.0-15.0% lactic acid, stirring in a magnetic stirrer until the chitosan is completely dissolved, adding the mixture into the mixed solution of the rice hull powder and the sodium hydroxide, adding 6-8% xanthan gum, 3-5% carrageenan, 20-25% sodium carboxymethylcellulose and 13-15% glycerol, stirring in a water bath kettle at the temperature of 60-70 ℃ for 40-50 minutes until the mixture is uniform, adding 4-5% allyl isothiocyanate while stirring, and cooling;
homogenizing in a high-pressure homogenizer at 20-26 ℃ under 115-125 MPa under 3 circulation conditions;
and step five, casting the mixture on a PC board to form a film, horizontally placing the film in an electrothermal blowing drying oven for drying, wherein the drying time is 180-300 min, the temperature is 40-60 ℃, and then cooling to room temperature to remove the film from the PC board, so as to obtain the degradable antibacterial film based on the rice hulls.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006118109A1 (en) * | 2005-04-27 | 2006-11-09 | Nihon University | Polysaccharide composite material |
| CN102504350A (en) * | 2011-10-11 | 2012-06-20 | 福建农林大学 | Degradable food packaging paper and preparation method thereof |
| CN102775647A (en) * | 2012-07-30 | 2012-11-14 | 昆明理工大学 | Preparation method of hemicellulose based edible film |
| CN105968405A (en) * | 2016-05-30 | 2016-09-28 | 天津工业大学 | Antimicrobial moisturizing degradable porous gel preservative film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105017544A (en) * | 2015-08-13 | 2015-11-04 | 江南大学 | Preparation of water-blocking biodegradable membrane containing low-viscosity rice-hull-based carboxymethyl cellulose |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006118109A1 (en) * | 2005-04-27 | 2006-11-09 | Nihon University | Polysaccharide composite material |
| CN102504350A (en) * | 2011-10-11 | 2012-06-20 | 福建农林大学 | Degradable food packaging paper and preparation method thereof |
| CN102775647A (en) * | 2012-07-30 | 2012-11-14 | 昆明理工大学 | Preparation method of hemicellulose based edible film |
| CN105968405A (en) * | 2016-05-30 | 2016-09-28 | 天津工业大学 | Antimicrobial moisturizing degradable porous gel preservative film and preparation method and application thereof |
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