CN108395582B - Cassava starch-polyvinyl alcohol-chitosan composite film and preparation method thereof - Google Patents
Cassava starch-polyvinyl alcohol-chitosan composite film and preparation method thereof Download PDFInfo
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- CN108395582B CN108395582B CN201810320944.5A CN201810320944A CN108395582B CN 108395582 B CN108395582 B CN 108395582B CN 201810320944 A CN201810320944 A CN 201810320944A CN 108395582 B CN108395582 B CN 108395582B
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- polyvinyl alcohol
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- 240000003183 Manihot esculenta Species 0.000 title claims abstract description 109
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 title claims abstract description 109
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229920002472 Starch Polymers 0.000 claims abstract description 53
- 239000008107 starch Substances 0.000 claims abstract description 53
- 235000019698 starch Nutrition 0.000 claims abstract description 53
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 50
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 50
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 42
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 42
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 42
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 66
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 239000012153 distilled water Substances 0.000 claims description 44
- 239000006185 dispersion Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000004580 weight loss Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011091 composite packaging material Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- 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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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Abstract
The invention relates to the technical field of film production, and particularly discloses a cassava starch-polyvinyl alcohol-chitosan composite film and a preparation method thereof. The cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight: 1.5-2.5 parts of cassava starch; 1.5-2.5 parts of polyvinyl alcohol; 0.5-1.0 part of chitosan; 2.5-3.0 parts of glycerol; 0.03-0.07 part of glutaraldehyde; nano SiO20.1-0.2 parts; 0.0005 to 0.003 portion of dispersant. The composite film provided by the invention has obviously improved mechanical strength such as tensile strength, elongation at break and the like, light transmittance and water absorption, is close to the existing non-degradable PE film, has good degradability under room temperature and natural conditions, has a weight loss rate of 50% in two months, and is nearly completely degraded in 8-10 months.
Description
Technical Field
The invention relates to the technical field of film production, in particular to a cassava starch-polyvinyl alcohol-chitosan composite film and a preparation method thereof.
Background
Along with the development, the use amount of non-biodegradable materials mainly made of plastics is greatly increased, so that more troubles are brought to people when the life is convenient, and the normal life of people is influenced. With the improvement of environmental awareness of people, biodegradable materials are also widely concerned in various aspects of the world.
The research on the starch/polyvinyl alcohol/chitosan composite film is more at home and abroad so far, wherein the research on the tapioca starch is less, the tapioca starch is basically corn starch or potato starch, and the tapioca starch/polyvinyl alcohol/chitosan composite film has wide and pollution-free raw material sources and can be completely degraded biologically, but the mechanical strength of the tapioca starch/polyvinyl alcohol/chitosan composite film does not meet the use requirement. The size of a dispersed phase in the nano material is 1/100 of the size of a traditional dispersed phase (0.1-1 um), the composite packaging material has more excellent performance than the original packaging material, and the research on the particle size and the dispersion condition of the nano material in a film and the control of the film structure is the key point of the current research.
Disclosure of Invention
Aiming at the problem that the mechanical strength such as tensile strength, elongation at break and the like of the existing composite film is far from meeting the use requirement, the invention provides a cassava starch-polyvinyl alcohol-chitosan composite film and a preparation method thereof.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
compared with the prior art, the cassava starch-polyvinyl alcohol-chitosan composite film provided by the invention is prepared by mixing the cassava starch, the polyvinyl alcohol and the chitosan, and adding the nano SiO2Simultaneously, the nano SiO is improved by adding a dispersant2So that nano SiO2A large amount of hydroxyl and unsaturated residual bonds on the surface are combined with a large amount of hydroxyl contained in polyvinyl alcohol, cassava starch and chitosan molecules to form hydrogen bonds, so that the nano SiO2Is better compatible with cassava starch, polyvinyl alcohol and chitosan, so that nano SiO is added2The composite film has obviously improved mechanical strength such as tensile strength, elongation at break and the like, light transmittance and water absorption rate, is close to the existing non-degradable PE film, has good degradability under room temperature and natural conditions, has a weight loss rate of 50% in two months, and is nearly completely degraded in 8-10 months.
Further, the invention also provides a preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film. The preparation method comprises the following steps:
(1) weighing the components according to the raw material formula of the cassava starch-polyvinyl alcohol-chitosan composite film;
(2) carrying out water bath stirring treatment on the cassava starch and distilled water to obtain a cassava starch solution;
(3) carrying out water bath stirring treatment on the polyvinyl alcohol and distilled water to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water are subjected to ultrasonic dispersion treatment to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid and a defoaming agent, adjusting the pH value to 3.0-4.0, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and after the membrane liquid is subjected to vacuum air exhaust treatment, casting the membrane liquid on a carrier, drying the carrier, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Compared with the prior art, the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film provided by the invention is simple in process, convenient to operate, safe, reliable and suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a cassava starch-polyvinyl alcohol-chitosan composite film. The cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the nanometer SiO of the embodiment of the invention2The film has a three-dimensional network structure, high toughness, corrosion resistance and high temperature resistance, and a large amount of hydroxyl and unsaturated residual bonds on the surface of the film are combined with a large amount of hydroxyl in polyvinyl alcohol, cassava starch and chitosan molecules to form hydrogen bonds, so that the mechanical property of the film is enhanced, and the tensile strength and the elongation at break are improved.
Preferably, the nano SiO2The particle size of (A) is 25-35 nm.
Preferably, the dispersing agent is sodium dodecyl benzene sulfonate, the surface energy of the nano material is large, the agglomeration phenomenon is easy to occur, the dispersibility of the nano material cannot be well exerted, and the nano SiO2The nano SiO particles can not be well dispersed in a matrix and can not play the role which the nano material should have, because of the alkyl long chain structure of the sodium dodecyl sulfate, when the dispersing system is added, the hydrophilic sulfonate extends into the water solution, the oleophylic alkyl long chain is adsorbed on the surface of the nano particles, thereby resisting particle agglomeration and ensuring that the dispersing system has better dispersion stability, therefore, the nano SiO particles are combined with the dispersing agent by adopting an ultrasonic method to add the dispersing agent2The dispersion is uniform, and the performance of the composite film is better improved.
Preferably, the dispersing agent is nano SiO20.5-1.5% of dry weight, ensuring that the nano SiO2The dispersion is uniform.
The cassava starch-polyvinyl alcohol-chitosan composite film provided by the embodiment of the invention is prepared by mixing cassava starch, polyvinyl alcohol and chitosan, wherein the cassava starch has good film forming property and biodegradability, the polyvinyl alcohol has strong thermal stability and high film forming property, can be degraded, has stable chemical property and high mechanical strength, and the chitosan has no toxic or side effect, can be degraded by microorganisms and has film forming property, so that the advantages of the cassava starch, the polyvinyl alcohol and the chitosan are fully utilized, the complementary advantages are realized, and the nano SiO is added2Simultaneously, the nano SiO is improved by adding a dispersant2So that nano SiO2A large amount of hydroxyl and unsaturated residual bonds on the surface are combined with a large amount of hydroxyl contained in polyvinyl alcohol, cassava starch and chitosan molecules to form hydrogen bonds, so that the nano SiO2Is better compatible with cassava starch, polyvinyl alcohol and chitosan, so that nano SiO is added2The composite film has obviously improved and improved mechanical strength such as tensile strength, elongation at break and the like, light transmittance and water absorption rate, is close to the prior non-degradable PE film, has good degradability under room temperature and natural conditions without adding a degradation additive, has a weight loss rate of 50% in two months, and is nearly completely degraded in 8-10 months.
The invention further provides a preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film on the premise of providing the cassava starch-polyvinyl alcohol-chitosan composite film.
In one embodiment, the preparation method comprises the following steps:
(1) weighing the components according to the raw material formula of the cassava starch-polyvinyl alcohol-chitosan composite film;
(2) carrying out water bath stirring treatment on the cassava starch and distilled water to obtain a cassava starch solution, wherein the distilled water is used for dissolving the cassava starch and can be evaporated in the drying treatment, so that the performance of the final composite film is not influenced;
(3) carrying out water bath stirring treatment on the polyvinyl alcohol and distilled water to obtain a polyvinyl alcohol solution, wherein the amount of the distilled water is enough to dissolve the polyvinyl alcohol, and the distilled water can be evaporated in the drying treatment, so that the performance of the final composite film is not influenced;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution to obtain a chitosan solution, wherein the acetic acid solution is used in an amount capable of dissolving the chitosan and can be evaporated in the drying treatment, so that the performance of the final composite film is not influenced;
(5) the nano SiO is added2Dispersing agent and distilled water are subjected to ultrasonic dispersion treatment to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid and a defoaming agent, adjusting the pH value to 3.0-4.0, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and after the membrane liquid is subjected to vacuum air exhaust treatment, casting the membrane liquid on a carrier, drying the carrier, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
The above preparation process is further explained below:
preferably, the defoaming agent is absolute ethyl alcohol, and bubbles in the film system are eliminated.
Preferably, the concentration of the acetic acid solution is 1moL/L, and the acetic acid solution is used for preparing the chitosan solution.
Preferably, hydrochloric acid and sodium hydroxide are adopted for adjusting the pH value, so that the pH value is maintained within a range of 3-4, and the stability of a film liquid system is ensured.
Preferably, in the step (2), the temperature of the water bath stirring treatment is 95 ℃ and the time is 25-35min, so that the cassava starch is fully dissolved to obtain the cassava starch solution.
Preferably, in the step (3), the temperature of the water bath stirring treatment is 80 ℃, and the time is 25-35min, so that the polyvinyl alcohol is fully dissolved to obtain the polyvinyl alcohol solution.
Preferably, in the step (4), the ultrasonic dispersion treatment time is 25-35min, so as to obtain the chitosan solution.
Preferably, in the step (5), the ultrasonic power of the ultrasonic dispersion treatment is 240W, the ultrasonic temperature is 50 ℃, and the ultrasonic dispersion treatment is carried out at ultra high temperatureThe sound time is 35-45min because of the low power of the nano SiO2The dispersion effect is not obvious, the dispersion effect of the nano SiO in the membrane liquid is not facilitated, and the nano SiO has a larger ultrasonic power2The particles are easy to agglomerate; with increasing temperature, nano SiO2The particle motion is intensified, the dispersion effect is good, but the temperature is over high, so that the nano SiO is generated2Nano SiO2The film cannot have good interaction with other components in the film liquid, so that the film performance effect is poor; the difference of ultrasonic time leads to nanometer SiO2The particles have different dispersion effects, and obvious resonance phenomenon can occur when the time is long; therefore, the above conditions are selected to ensure the nano SiO2To obtain nano SiO2Dispersing liquid, and optimizing the comprehensive performance of the obtained film.
Preferably, in the step (7), the temperature of the drying treatment is 70 ℃, which is beneficial to curing the film.
Preferably, the nano SiO2Is 1.5 to 2.0 percent of the dry weight of the cassava starch-polyvinyl alcohol-chitosan composite film, and ensures that the added nano SiO is added2And (4) the purpose of improving the performance of the film is achieved.
Further preferably, the nano SiO2Is 1.5 percent of the dry weight of the cassava starch-polyvinyl alcohol-chitosan composite film, at the moment, the nano SiO is2The particles are uniformly placed in the cassava starch particles, the interaction is obvious, the tensile strength of the film is improved to the maximum, and the elongation at break performance is the best.
The method has simple preparation process, convenient operation, safety and reliability, and is suitable for industrial production.
In order to better illustrate the tapioca starch-polyvinyl alcohol-chitosan composite film and the preparation method thereof provided by the embodiments of the present invention, the following examples further illustrate the tapioca starch-polyvinyl alcohol-chitosan composite film.
Example 1
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 25min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 25min to obtain a polyvinyl alcohol solution;
(4) carrying out ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 25min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 35min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 3.5, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Example 2
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 35min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 35min to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 35min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 45min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 3.5, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Example 3
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 35min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 35min to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 35min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 45min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 4.0, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Example 4
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 30min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 30min to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 30min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 40min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtainNano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 3.5, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Example 5
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 30min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 30min to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 30min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 40min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain the nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 3.5, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Example 6
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 25min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 25min to obtain a polyvinyl alcohol solution;
(4) carrying out ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 25min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 35min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 3.0, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
Example 7
A cassava starch-polyvinyl alcohol-chitosan composite film comprises the following raw material components in parts by weight:
the preparation method of the cassava starch-polyvinyl alcohol-chitosan composite film comprises the following steps:
(1) weighing the components according to the raw material ratio;
(2) carrying out water bath on the cassava starch and distilled water at 95 ℃, and stirring for 35min to obtain a cassava starch solution;
(3) carrying out water bath on the polyvinyl alcohol and distilled water at 80 ℃, and stirring for 35min to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution for 35min to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 45min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid with a small amount of absolute ethyl alcohol, adjusting the pH to 3.5, adding distilled water to a constant volume, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and (3) carrying out vacuum air exhaust treatment on the membrane liquid until no bubbles exist in the solution, casting the membrane liquid onto a carrier, drying the membrane liquid in an oven at 70 ℃, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
To better illustrate the characteristics of the tapioca starch-polyvinyl alcohol-chitosan composite films provided in the examples of the present invention, the films prepared in examples 1 to 7 were tested for their respective properties, and the results are shown in table 1.
TABLE 1
From the data, the composite film prepared in the embodiment of the invention has the advantages that the tensile strength, the elongation at break, the light transmittance and other properties are all superior to or approximate to those of the existing non-degradable material PE film, and the prepared composite film can be biodegraded without adding a degradation assistant. The composite film has good degradability under room temperature and natural conditions, the weight loss rate reaches 50% in two months, and the composite film is almost completely degraded in 8-10 months.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A cassava starch-polyvinyl alcohol-chitosan composite film is characterized in that: the material comprises the following raw material components in parts by weight:
2.0 parts of cassava starch;
2.0 parts of polyvinyl alcohol;
0.67 part of chitosan;
3.0 parts of glycerol;
0.05 part of glutaraldehyde;
nano SiO20.2 part;
0.002 part of dispersant;
85 parts of distilled water;
10 parts of acetic acid solution;
also comprises a raw material component of a defoaming agent,
the dispersing agent is sodium dodecyl benzene sulfonate,
the cassava starch-polyvinyl alcohol-chitosan composite film is prepared by the following method,
(1) weighing the components according to the raw material formula of the cassava starch-polyvinyl alcohol-chitosan composite film;
(2) carrying out water bath stirring treatment on the cassava starch and distilled water to obtain a cassava starch solution;
(3) carrying out water bath stirring treatment on the polyvinyl alcohol and distilled water to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 35min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid and a defoaming agent, adjusting the pH value to 3.0-4.0, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and after the membrane liquid is subjected to vacuum air exhaust treatment, casting the membrane liquid on a carrier, drying the carrier, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
2. The tapioca starch-polyvinyl alcohol-chitosan composite film according to claim 1, wherein: the nano SiO2The particle size of (A) is 25-35 nm.
3. A preparation method of a cassava starch-polyvinyl alcohol-chitosan composite film is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing the components according to the raw material formula of the cassava starch-polyvinyl alcohol-chitosan composite film as claimed in claim 1 or 2;
(2) carrying out water bath stirring treatment on the cassava starch and distilled water to obtain a cassava starch solution;
(3) carrying out water bath stirring treatment on the polyvinyl alcohol and distilled water to obtain a polyvinyl alcohol solution;
(4) performing ultrasonic dispersion treatment on the chitosan and an acetic acid solution to obtain a chitosan solution;
(5) the nano SiO is added2Dispersing agent and distilled water, and performing ultrasonic dispersion treatment for 35min under the conditions that the ultrasonic power is 240W and the ultrasonic temperature is 50 ℃ to obtain nano SiO2A dispersion liquid;
(6) mixing the cassava starch solution, the polyvinyl alcohol solution, the chitosan solution and the nano SiO2Mixing the dispersion liquid and a defoaming agent, adjusting the pH value to 3.0-4.0, and adding the glycerol and the glutaraldehyde to obtain a membrane liquid;
(7) and after the membrane liquid is subjected to vacuum air exhaust treatment, casting the membrane liquid on a carrier, drying the carrier, and stripping the membrane from the carrier after the membrane is solidified to obtain the cassava starch-polyvinyl alcohol-chitosan composite membrane.
4. The method for preparing a tapioca starch-polyvinyl alcohol-chitosan composite film according to claim 3, wherein: the defoaming agent is absolute ethyl alcohol.
5. The method for preparing a tapioca starch-polyvinyl alcohol-chitosan composite film according to claim 3, wherein: the concentration of the acetic acid solution is 1 moL/L.
6. The method for preparing a tapioca starch-polyvinyl alcohol-chitosan composite film according to claim 3, wherein: hydrochloric acid and sodium hydroxide are adopted for adjusting the pH.
7. The method for preparing a tapioca starch-polyvinyl alcohol-chitosan composite film according to claim 3, wherein: in the step (2), the temperature of the water bath stirring treatment is 95 ℃, the time is 25-35min, and/or
In the step (3), the temperature of the water bath stirring treatment is 80 ℃, the time is 25-35min, and/or
In the step (4), the time of ultrasonic dispersion treatment is 25-35min, and/or
In the step (7), the temperature of the drying treatment is 70 ℃.
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| JP2016053160A (en) * | 2014-09-02 | 2016-04-14 | 日化精工株式会社 | Film |
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| JP2016053160A (en) * | 2014-09-02 | 2016-04-14 | 日化精工株式会社 | Film |
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