CN110776673A - Jelly packaging shell capable of being rapidly degraded - Google Patents
Jelly packaging shell capable of being rapidly degraded Download PDFInfo
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- CN110776673A CN110776673A CN201911129770.5A CN201911129770A CN110776673A CN 110776673 A CN110776673 A CN 110776673A CN 201911129770 A CN201911129770 A CN 201911129770A CN 110776673 A CN110776673 A CN 110776673A
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- 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
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/03—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a quickly degradable jelly packaging shell, which is prepared by the following steps: 1) preparing an ascorbic acid/cyclodextrin inclusion compound by adopting ascorbic acid and cyclodextrin; 2) preparing polymer microspheres by using monomer acrylamide and acrylic acid as raw materials; 3) preparing modified polymer microspheres by using an ascorbic acid/cyclodextrin inclusion compound and polymer microspheres as raw materials; 4) and uniformly stirring the prepared raw materials at a high speed, adding the uniformly stirred raw materials into a double-screw extruder, melting and blending the uniformly stirred raw materials, putting the uniformly stirred raw materials into a template, and pressing the uniformly stirred raw materials into a blank to obtain the required jelly packaging shell. The jelly packaging shell can reduce the oxidation-reduction potential in the soil environment and provide a proper growth environment for the initial growth of microorganisms, so that the rapid growth and mass propagation of the microorganisms in the soil can be promoted, the degradation speed of the packaging shell can be accelerated, and the rapid full degradation of the packaging shell can be realized.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a jelly packaging shell capable of being rapidly degraded.
Background
Jelly is a leisure food which is popular with people, and is a jelly food which is generally processed by taking water, edible seaweed gel or other edible vegetable gum, sugar, food additives and the like as raw materials through the working procedures of sol, blending, filling, sterilization, cooling and the like. With the continuous improvement of the requirements of people on food, the jelly is rich and balanced in nutrition, good in taste and flavor, convenient to carry and easy to stimulate the appetite due to the addition of the components with the health-care effect, so that the jelly is more and more valued and loved by consumers.
Along with the pursuit of more and more consumers of jelly, the packaging shell garbage generated after eating the jelly brings great burden to the environment, so that the degradability of the jelly packaging shell is improved, and the rapid degradation of the jelly packaging shell becomes the focus of research of technicians. Chinese patent CN2019100297627 discloses a polylactic acid-starch-PVA composite degradable packaging film and a preparation method thereof, wherein four high polymers of modified corn starch, polyvinyl alcohol, polylactic acid and chitosan are used as main raw materials, pectin and nano organic bentonite are used as a composite cross-linking agent, so that the degradable packaging film is prepared, the degradation of the packaging film is realized by mainly utilizing microorganisms in soil, but the degradation speed of the packaging film is greatly related to the growth and reproduction speed of the microorganisms after the degradation speed is degraded by utilizing the microorganisms, and the degradation speed of the packaging film can be improved only after the microorganisms in the soil grow and reproduce to a certain degree, so the degradation by utilizing the microorganisms often has the defects of low degradation speed at the early stage and long degradation period, and the rapid degradation cannot be realized; chinese patent CN2014100680166 discloses a preparation method of a doped modified titanium dioxide/graphene composite material, which can play a role in catalyzing and degrading organic pollutants under ultraviolet light, visible light and even infrared light conditions, and the composite material is added into a packaging shell to realize rapid degradation of the packaging shell, but because the composite material belongs to a composite photocatalyst and can play a role in playing a role under a light condition, the composite material cannot play a role in improving degradation speed of plastic wastes in a dark place.
Disclosure of Invention
The invention aims to solve the existing problems and provides a quickly degradable jelly packaging shell, which can reduce the oxidation-reduction potential in the soil environment to a certain extent by improving the raw materials, so that the quick and large-scale growth and propagation of microorganisms are promoted, the degradation speed of the packaging shell is increased, and the quick degradation is realized.
The invention is realized by the following technical scheme:
a quickly degradable jelly packaging shell is specifically prepared by the following steps:
1) adding ascorbic acid into deionized water, stirring for dissolving to obtain an ascorbic acid solution, then adding a cyclodextrin saturated aqueous solution at a certain temperature, stirring for 2-3h at the rotation speed of 120-170r/min, cooling to room temperature, then placing in a refrigerator for cooling and crystallizing for 20-30h, taking out, carrying out suction filtration and water washing, and placing the obtained product in a drying oven at the temperature of 45-55 ℃ for drying for 5-8h to obtain an ascorbic acid/cyclodextrin inclusion compound; the ascorbic acid adopted in the invention has good reducibility, can effectively reduce the oxidation-reduction potential of the soil environment, and can provide a proper low oxidation-reduction potential environment for the growth of microorganisms, thereby being beneficial to the rapid growth and reproduction of the microorganisms;
2) adding monomer acrylamide and acrylic acid into distilled water, dropwise adding sodium hydroxide to adjust the pH value to 9-10, then adding N, N-methylene bisacrylamide and a sodium bisulfite solution, then adding liquid paraffin, Tween 60, span 80 and N-butyl alcohol, heating and stirring in a water bath at 50-60 ℃ for 3-7min, then adding ammonium persulfate, reacting at constant temperature for 4-6h, standing the product for 5-7h, and washing and drying after suction filtration to obtain polymer microspheres; acrylamide and acrylic acid are used as comonomers, and a reverse microemulsion polymerization method is adopted to prepare the nano-scale polymer elastic microspheres, so that the elasticity of a packaging shell is improved, the jelly can be eaten by light extrusion when being eaten, and the eating convenience of the jelly is improved;
3) adding the prepared polymer microspheres into dichloromethane, adding 4-dimethylaminopyridine after dissolution, slowly adding triethylamine and 2-bromoisobutyryl bromide dropwise in an ice water bath, stirring for 1-2h at the rotation speed of 80-120r/min, heating to room temperature, continuing stirring for 10-15h, filtering, washing and drying the product, adding the product, carbonyldiimidazole and 4-dimethylaminopyridine into dry dimethyl sulfoxide, reacting for 5-8h at room temperature, washing and drying the product, adding the product into an anhydrous dimethyl sulfoxide solution containing an ascorbic acid/cyclodextrin inclusion compound and 4-dimethylaminopyridine, reacting for 15-20h at room temperature in a dark place, and filtering and drying to obtain the modified polymer microspheres modified by the ascorbic acid/cyclodextrin inclusion compound; the ascorbic acid/cyclodextrin inclusion compound is adopted to modify the polymer microspheres, and the high-density ascorbic acid/cyclodextrin inclusion compound is introduced to the surfaces of the polymer microspheres, so that the stability and the adhesion performance of the polymer microspheres can be improved, the improvement of the bonding strength among the raw material components of the packaging shell is facilitated, and the compactness of the packaging shell is improved;
4) adding plant starch, sodium silicate, magnesium oxalate, polylactic acid, polyamide and modified polymer microspheres into a high-speed mixer, stirring for 2-5min, slowly adding a proper amount of sorbitol, continuously stirring for 5-8min, uniformly stirring, adding into a double-screw extruder, melting and blending, putting into a template, and pressing to obtain a required jelly packaging shell; the added sodium silicate can improve the alkalinity of the soil environment and promote the reduction range of the oxidation-reduction potential in the soil environment; the added magnesium oxalate is dissolved in the water body of the soil to free magnesium ions, so that the water hardness of the soil can be improved, and the reduction range of the oxidation-reduction potential in the soil environment can be further improved, thereby promoting the growth and the propagation of microorganisms and accelerating the degradation speed of the packaging shell.
Preferably, the rapidly degradable jelly packaging shell is characterized in that in the preparation step 1), the mass fraction of the ascorbic acid solution is 5-9%, the mass ratio of ascorbic acid to cyclodextrin is 1:3-5, the temperature of the saturated aqueous solution of cyclodextrin is 50-70 ℃, the cyclodextrin is β -cyclodextrin, and the temperature of cooling crystallization is 2-5 ℃.
Preferably, in the preparation step 2), the concentration of the sodium bisulfite solution is 0.8-1.5%, and the mass ratio of the sodium bisulfite solution to acrylamide, acrylic acid, N-methylene bisacrylamide, liquid paraffin, tween 60, span 80 and N-butanol is 1:37-43:14-17:0.5-0.8:75-85:15-18:23-26: 3-5; the addition amount of the ammonium persulfate is 0.3-0.8% of the total weight of the reaction system; the drying temperature is 50-60 ℃, and the drying time is 3-6 h.
Preferably, the jelly packaging shell capable of being rapidly degraded is prepared in the step 3), wherein the mass-to-volume ratio of the polymer microspheres to 4-dimethylaminopyridine, triethylamine and 2-bromoisobutyryl bromide in dichloromethane is 1g: 28-34 ml: 0.05-0.08 g: 1.2-1.4 ml: 0.5-0.8 ml; the mass-volume ratio of the product after suction filtration, washing and drying to the carbonyldiimidazole, 4-dimethylaminopyridine and dried dimethyl sulfoxide is 1g: 0.21-0.25g, 0.15-0.18 g: 25-30 ml; the mass volume ratio of the washed and dried product to the anhydrous dimethyl sulfoxide solution is 1:30-40g/ml, wherein the content of the ascorbic acid/cyclodextrin inclusion compound in the anhydrous dimethyl sulfoxide solution is 10-18%, and the content of 4-dimethylaminopyridine is 3-6%; the washing is carried out for 5-6 times by adopting dried dichloromethane, acetone and methanol in turn; the drying temperature is 55-65 ℃, and the drying time is 10-13 h.
Preferably, the jelly packaging shell capable of being rapidly degraded is prepared by the following steps of 4), wherein in the preparation step, the weight ratio of at least one of the plant starch selected from corn starch, wheat starch and sweet potato starch to the sodium silicate, the magnesium oxalate, the polylactic acid, the polyamide, the modified polymer microspheres and the sorbitol is 35-45:1-2:0.3-0.8:15-20:0.2-0.5:3-7: 5-9; the rotating speed of the high-speed mixer is 600-900 r/min; the double-screw extruder is divided into four temperature zones, namely a first zone of 140-; the above-mentionedThe temperature of the template compact is 160-165 ℃, and the pressure is 21-24Kg/cm
2And the compacting time is 3-6 min.
Compared with the prior art, the invention has the following advantages:
according to the jelly packaging shell prepared by the invention, by utilizing the characteristic that anaerobic microorganisms and facultative anaerobic microorganisms which are widely distributed in a soil environment are suitable for growing in a low oxidation-reduction potential environment, a growth environment with a suitable low oxidation-reduction potential is provided for the initial growth of the microorganisms by adding the reducing ascorbic acid, the sodium silicate and the magnesium oxalate which can improve the alkalinity of the soil environment and the hardness of a water body into the raw material components, so that the rapid growth and mass propagation of the microorganisms in the soil can be promoted, the degradation speed of the packaging shell can be accelerated, and the rapid full degradation of the packaging shell can be realized.
Detailed Description
The present invention will be further described with reference to specific embodiments.
Example 1
A quickly degradable jelly packaging shell is specifically prepared by the following steps:
1) adding ascorbic acid into deionized water, stirring for dissolving to obtain an ascorbic acid solution, then adding a cyclodextrin saturated aqueous solution at a certain temperature, stirring for 3 hours at a rotation speed of 120r/min, cooling to room temperature, then placing in a refrigerator for cooling and crystallizing for 20 hours, taking out, carrying out suction filtration and water washing, and placing the obtained product in a 45 ℃ oven for drying for 8 hours to obtain an ascorbic acid/cyclodextrin inclusion compound;
2) adding monomer acrylamide and acrylic acid into distilled water, dropwise adding sodium hydroxide to adjust the pH value to 9, then adding N, N-methylene bisacrylamide and a sodium bisulfite solution, then adding liquid paraffin, tween 60, span 80 and N-butyl alcohol, heating and stirring in a water bath at 50 ℃ for 7min, then adding ammonium persulfate, reacting at constant temperature for 6h, standing the product for 7h, and washing and drying after suction filtration to obtain polymer microspheres;
3) adding the prepared polymer microspheres into dichloromethane, adding 4-dimethylaminopyridine after dissolution, slowly adding triethylamine and 2-bromoisobutyryl bromide dropwise in an ice-water bath, stirring for 2 hours at the rotating speed of 80r/min, heating to room temperature, continuing stirring for 15 hours, carrying out suction filtration, washing and drying on the product, adding the product, carbonyldiimidazole and 4-dimethylaminopyridine into dry dimethyl sulfoxide, reacting for 5 hours at room temperature, washing and drying the product, adding the product into an anhydrous dimethyl sulfoxide solution containing an ascorbic acid/cyclodextrin inclusion compound and 4-dimethylaminopyridine, carrying out dark reaction for 15 hours at room temperature, and carrying out suction filtration and drying to obtain modified polymer microspheres;
4) adding plant starch, sodium silicate, magnesium oxalate, polylactic acid, polyamide and modified polymer microspheres into a high-speed mixer, stirring for 5min, slowly adding a proper amount of sorbitol, continuously stirring for 8min, uniformly stirring, adding into a double-screw extruder, melting and blending, putting into a template, and pressing into a blank to obtain the required jelly packaging shell.
Preferably, in the preparation step 1), the mass fraction of the ascorbic acid solution is 5%, the mass ratio of ascorbic acid to cyclodextrin is 1:3, the temperature of the cyclodextrin saturated aqueous solution is 50 ℃, the cyclodextrin is β -cyclodextrin, and the temperature of cooling crystallization is 2 ℃.
Preferably, in the preparation step 2), the concentration of the sodium bisulfite solution is 0.8%, and the mass ratio of the sodium bisulfite solution to the acrylamide, the acrylic acid, the N, N-methylene-bisacrylamide, the liquid paraffin, the Tween 60, the span 80 and the N-butanol is 1:37:14:0.5:75:15:23: 3; the adding amount of the ammonium persulfate is 0.3 percent of the total weight of the reaction system; the drying temperature is 50 ℃, and the drying time is 6 h.
Preferably, in the preparation step 3), the mass-to-volume ratio of the polymer microsphere, 4-dimethylaminopyridine, triethylamine and 2-bromoisobutyryl bromide in dichloromethane is 1g: 28 ml: 0.05 g: 1.2 ml: 0.5 ml; the mass-volume ratio of the product after suction filtration, washing and drying to the carbonyldiimidazole, 4-dimethylaminopyridine and dried dimethyl sulfoxide is 1g: 0.21g:0.15 g: 25 ml; the mass-volume ratio of the washed and dried product to the anhydrous dimethyl sulfoxide solution is 1:30g/ml, wherein the content of the ascorbic acid/cyclodextrin inclusion compound in the anhydrous dimethyl sulfoxide solution is 10%, and the content of 4-dimethylaminopyridine is 3%; the washing is carried out for 5 times by adopting dried dichloromethane, acetone and methanol in turn; the drying temperature is 55 ℃, and the drying time is 13 h.
Preferably, in the preparation step 4), the plant starch is selected from at least one of corn starch, wheat starch and sweet potato starch, and the weight ratio of the plant starch to the sodium silicate, the magnesium oxalate, the polylactic acid, the polyamide, the modified polymer microspheres and the sorbitol is 35:1:0.3:15:0.2:3: 5; the rotating speed of the high-speed mixer is 600 r/min; the double-screw extruder is divided into four temperature zones, namely a first zone of 140 ℃, a second zone of 155 ℃, a third zone of 175 ℃ and a fourth zone of 195 ℃; the temperature of the template compact is 160 ℃, and the pressure is 21Kg/cm
2And the compacting time is 6 min.
Example 2
A quickly degradable jelly packaging shell is specifically prepared by the following steps:
1) adding ascorbic acid into deionized water, stirring for dissolving to obtain an ascorbic acid solution, then adding a cyclodextrin saturated aqueous solution at a certain temperature, stirring for 2.5h at the rotation speed of 150r/min, cooling to room temperature, then placing in a refrigerator for cooling and crystallizing for 25h, taking out, carrying out suction filtration and water washing, and placing the obtained product in a 50 ℃ oven for drying for 7h to obtain an ascorbic acid/cyclodextrin inclusion compound;
2) adding monomer acrylamide and acrylic acid into distilled water, dropwise adding sodium hydroxide to adjust the pH value to 9.5, then adding N, N-methylene bisacrylamide and a sodium bisulfite solution, then adding liquid paraffin, Tween 60, span 80 and N-butyl alcohol, heating and stirring for 5min in a water bath at 55 ℃, then adding ammonium persulfate, reacting for 5h at constant temperature, standing the product for 6h, and washing and drying after suction filtration to obtain polymer microspheres;
3) adding the prepared polymer microspheres into dichloromethane, adding 4-dimethylaminopyridine after dissolution, slowly adding triethylamine and 2-bromoisobutyryl bromide dropwise in an ice-water bath, stirring for 1.5h at the rotation speed of 100r/min, heating to room temperature, then continuously stirring for 13h, carrying out suction filtration, washing and drying on the product, adding the product, carbonyldiimidazole and 4-dimethylaminopyridine into dry dimethyl sulfoxide, reacting for 6h at room temperature, washing and drying the product, adding the product into an anhydrous dimethyl sulfoxide solution containing an ascorbic acid/cyclodextrin inclusion compound and 4-dimethylaminopyridine, reacting for 18h in a dark place at room temperature, and carrying out suction filtration and drying to obtain modified polymer microspheres;
4) adding plant starch, sodium silicate, magnesium oxalate, polylactic acid, polyamide and modified polymer microspheres into a high-speed mixer, stirring for 3min, slowly adding a proper amount of sorbitol, continuously stirring for 7min, uniformly stirring, adding into a double-screw extruder, melting and blending, putting into a template, and pressing into a blank to obtain the required jelly packaging shell.
Preferably, in the preparation step 1), the mass fraction of the ascorbic acid solution is 6%, the mass ratio of ascorbic acid to cyclodextrin is 1:4, the temperature of the cyclodextrin saturated aqueous solution is 60 ℃, the cyclodextrin is β -cyclodextrin, and the temperature of cooling crystallization is 3 ℃.
Preferably, in the preparation step 2), the concentration of the sodium bisulfite solution is 1.2%, and the mass ratio of the sodium bisulfite solution to the acrylamide, the acrylic acid, the N, N-methylene-bisacrylamide, the liquid paraffin, the Tween 60, the span 80 and the N-butanol is 1:40:15:0.7:80:16:25: 4; the adding amount of the ammonium persulfate is 0.5 percent of the total weight of the reaction system; the drying temperature is 55 ℃, and the drying time is 4 h.
Preferably, in the preparation step 3), the mass-to-volume ratio of the polymer microsphere, 4-dimethylaminopyridine, triethylamine and 2-bromoisobutyryl bromide in dichloromethane is 1g: 31 ml: 0.07 g: 1.3 ml: 0.6 ml; the mass-volume ratio of the product after suction filtration, washing and drying to the carbonyldiimidazole, 4-dimethylaminopyridine and dried dimethyl sulfoxide is 1g: 0.23g:0.16 g: 27 ml; the mass-volume ratio of the washed and dried product to the anhydrous dimethyl sulfoxide solution is 1:35g/ml, wherein the content of the ascorbic acid/cyclodextrin inclusion compound in the anhydrous dimethyl sulfoxide solution is 14%, and the content of 4-dimethylaminopyridine is 5%; the washing is carried out for 5 times by adopting dried dichloromethane, acetone and methanol in turn; the drying temperature is 60 ℃, and the drying time is 11 h.
As a preferenceIn the preparation step 4), the plant starch is selected from at least one of corn starch, wheat starch and sweet potato starch, and the weight ratio of the plant starch to sodium silicate, magnesium oxalate, polylactic acid, polyamide, modified polymer microspheres and sorbitol is 40:1.5:0.5:18:0.3:5: 7; the rotating speed of the high-speed mixer is 700 r/min; the double-screw extruder is divided into four temperature zones, namely a first zone of 143 ℃, a second zone of 158 ℃, a third zone of 177 ℃ and a fourth zone of 196 ℃; the temperature of the template compact is 162 ℃, and the pressure is 23Kg/cm
2And compacting time is 5 min.
Example 3
A quickly degradable jelly packaging shell is specifically prepared by the following steps:
1) adding ascorbic acid into deionized water, stirring for dissolving to obtain an ascorbic acid solution, then adding a cyclodextrin saturated aqueous solution at a certain temperature, stirring for 2 hours at the rotating speed of 170r/min, cooling to room temperature, then placing in a refrigerator for cooling and crystallizing for 30 hours, taking out, carrying out suction filtration and water washing, and placing the obtained product in a 55 ℃ oven for drying for 5 hours to obtain an ascorbic acid/cyclodextrin inclusion compound;
2) adding monomer acrylamide and acrylic acid into distilled water, dropwise adding sodium hydroxide to adjust the pH value to 10, then adding N, N-methylene bisacrylamide and a sodium bisulfite solution, then adding liquid paraffin, tween 60, span 80 and N-butyl alcohol, heating and stirring in a water bath at 60 ℃ for 3min, then adding ammonium persulfate, reacting at constant temperature for 4h, standing the product for 5h, and washing and drying after suction filtration to obtain polymer microspheres;
3) adding the prepared polymer microspheres into dichloromethane, adding 4-dimethylaminopyridine after dissolution, slowly adding triethylamine and 2-bromoisobutyryl bromide dropwise in an ice-water bath, stirring for 1h at the rotating speed of 120r/min, heating to room temperature, continuing stirring for 10h, carrying out suction filtration, washing and drying on the product, adding the product, carbonyldiimidazole and 4-dimethylaminopyridine into dry dimethyl sulfoxide, reacting for 8h at room temperature, washing and drying the product, adding the product into an anhydrous dimethyl sulfoxide solution containing an ascorbic acid/cyclodextrin inclusion compound and 4-dimethylaminopyridine, carrying out dark reaction for 20h at room temperature, and carrying out suction filtration and drying to obtain modified polymer microspheres;
4) adding plant starch, sodium silicate, magnesium oxalate, polylactic acid, polyamide and modified polymer microspheres into a high-speed mixer, stirring for 2min, slowly adding a proper amount of sorbitol, continuously stirring for 5min, uniformly stirring, adding into a double-screw extruder, melting and blending, putting into a template, and pressing into a blank to obtain the required jelly packaging shell.
Preferably, in the preparation step 1), the mass fraction of the ascorbic acid solution is 9%, the mass ratio of ascorbic acid to cyclodextrin is 1:5, the temperature of the cyclodextrin saturated aqueous solution is 70 ℃, the cyclodextrin is β -cyclodextrin, and the temperature of cooling crystallization is 5 ℃.
Preferably, in the preparation step 2), the concentration of the sodium bisulfite solution is 1.5%, and the mass ratio of the sodium bisulfite solution to the acrylamide, the acrylic acid, the N, N-methylene-bisacrylamide, the liquid paraffin, the Tween 60, the span 80 and the N-butanol is 1:43:17:0.8:85:18:26: 5; the adding amount of the ammonium persulfate is 0.8 percent of the total weight of the reaction system; the drying temperature is 60 ℃, and the drying time is 3 h.
Preferably, in the preparation step 3), the mass-to-volume ratio of the polymer microsphere, 4-dimethylaminopyridine, triethylamine and 2-bromoisobutyryl bromide in dichloromethane is 1g: 34 ml: 0.08 g: 1.4 ml: 0.8 ml; the mass volume ratio of the product after being filtered, washed and dried to the carbonyldiimidazole, 4-dimethylaminopyridine and dried dimethyl sulfoxide is 1g:0.25g:0.18g:30 ml; the mass-volume ratio of the washed and dried product to the anhydrous dimethyl sulfoxide solution is 1:40g/ml, wherein the content of the ascorbic acid/cyclodextrin inclusion compound in the anhydrous dimethyl sulfoxide solution is 18%, and the content of 4-dimethylaminopyridine is 6%; the washing is carried out for 6 times by adopting dried dichloromethane, acetone and methanol in turn; the drying temperature is 65 ℃, and the drying time is 10 h.
Preferably, in the preparation step 4), the plant starch is selected from at least one of corn starch, wheat starch and sweet potato starch, and the weight of sodium silicate, magnesium oxalate, polylactic acid, polyamide, modified polymer microspheres and sorbitolThe amount ratio is 45:2:0.8:20:0.5:7: 9; the rotating speed of the high-speed mixer is 900 r/min; the double-screw extruder is divided into four temperature zones, namely a first zone of 145 ℃, a second zone of 160 ℃, a third zone of 180 ℃ and a fourth zone of 200 ℃; the temperature of the template compact is 165 ℃, and the pressure is 24Kg/cm
2And the compacting time is 3 min.
Control group: the degraded plastic prepared in example 1 disclosed in chinese patent CN 2010102105137.
Test example: plastic sheets with the same specification are prepared by the technical methods disclosed in the example 1 and the control group respectively, the size is 10cm multiplied by 10cm, the thickness is 0.5cm, the prepared plastic sheets are put into compost, activated sludge and soil according to the weight ratio of 1%, the samples are taken every 10 days, the quality loss (five parallel samples in each sample) is recorded in turn, the samples are continuously taken for 80 days, and the formula of the quality loss rate is as follows: s = (m0-mt)/m0 × 100%, where m0 is the mass of the plastic sheet before degradation and mt is the mass of the plastic sheet after t days of degradation, and the mass loss of each plastic sheet was recorded, and the results are as follows:
note: at the time the test proceeded to 120d, the plastic sheet in example 1 was completely degraded; at 150d, the plastics sheets in comparative examples 2 and 3 were completely degraded; at the time the test proceeded to 180d, the plastic sheet in comparative example 1 was completely degraded; at 190d, the plastic sheets in the control group were completely degraded;
from the above table, it can be seen that the plastic sheet prepared by the technical scheme provided by the invention has the characteristic of high degradation rate compared with the degradable plastic sheet prepared by the prior art, is especially obvious in the early stage of degradation, and has good market popularization and application prospects.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention.
Claims (5)
1. A quickly degradable jelly packaging shell is characterized by comprising the following specific preparation methods:
1) adding ascorbic acid into deionized water, stirring for dissolving to obtain an ascorbic acid solution, then adding a cyclodextrin saturated aqueous solution at a certain temperature, stirring for 2-3h at the rotation speed of 120-170r/min, cooling to room temperature, then placing in a refrigerator for cooling and crystallizing for 20-30h, taking out, carrying out suction filtration and water washing, and placing the obtained product in a drying oven at the temperature of 45-55 ℃ for drying for 5-8h to obtain an ascorbic acid/cyclodextrin inclusion compound;
2) adding monomer acrylamide and acrylic acid into distilled water, dropwise adding sodium hydroxide to adjust the pH value to 9-10, then adding N, N-methylene bisacrylamide and a sodium bisulfite solution, then adding liquid paraffin, Tween 60, span 80 and N-butyl alcohol, heating and stirring in a water bath at 50-60 ℃ for 3-7min, then adding ammonium persulfate, reacting at constant temperature for 4-6h, standing the product for 5-7h, and washing and drying after suction filtration to obtain polymer microspheres;
3) adding the prepared polymer microspheres into dichloromethane, adding 4-dimethylaminopyridine after dissolution, slowly adding triethylamine and 2-bromoisobutyryl bromide dropwise in an ice water bath, stirring for 1-2h at the rotation speed of 80-120r/min, heating to room temperature, continuing stirring for 10-15h, filtering, washing and drying the product, adding the product, carbonyldiimidazole and 4-dimethylaminopyridine into dry dimethyl sulfoxide, reacting for 5-8h at room temperature, washing and drying the product, adding the product into an anhydrous dimethyl sulfoxide solution containing an ascorbic acid/cyclodextrin inclusion compound and 4-dimethylaminopyridine, reacting for 15-20h at room temperature in a dark place, and filtering and drying to obtain the modified polymer microspheres modified by the ascorbic acid/cyclodextrin inclusion compound;
4) adding plant starch, sodium silicate, magnesium oxalate, polylactic acid, polyamide and modified polymer microspheres into a high-speed mixer, stirring for 2-5min, slowly adding a proper amount of sorbitol, continuously stirring for 5-8min, uniformly stirring, adding into a double-screw extruder, melting and blending, putting into a template, and pressing into a blank to obtain the required jelly packaging shell.
2. The rapidly degradable jelly packaging shell according to claim 1, wherein in the preparation step 1), the ascorbic acid solution is 5-9% by mass, wherein the mass ratio of ascorbic acid to cyclodextrin is 1:3-5, the temperature of the saturated aqueous solution of cyclodextrin is 50-70 ℃, wherein the cyclodextrin is β -cyclodextrin, and the temperature of cooling crystallization is 2-5 ℃.
3. The rapidly degradable jelly packaging shell according to claim 1, wherein in the preparation step 2), the concentration of the sodium bisulfite solution is 0.8-1.5% and the mass ratio of acrylamide, acrylic acid, N-methylenebisacrylamide, liquid paraffin, Tween 60, span 80 and N-butanol is 1:37-43:14-17:0.5-0.8:75-85:15-18:23-26: 3-5; the addition amount of the ammonium persulfate is 0.3-0.8% of the total weight of the reaction system; the drying temperature is 50-60 ℃, and the drying time is 3-6 h.
4. The rapidly degradable jelly packaging shell according to claim 1, wherein in the preparation step 3), the mass-to-volume ratio of the polymer microspheres, 4-dimethylaminopyridine, triethylamine and 2-bromoisobutyryl bromide in dichloromethane is 1g: 28-34 ml: 0.05-0.08 g: 1.2-1.4 ml: 0.5-0.8 ml; the mass-volume ratio of the product after suction filtration, washing and drying to the carbonyldiimidazole, 4-dimethylaminopyridine and dried dimethyl sulfoxide is 1g: 0.21-0.25g, 0.15-0.18 g: 25-30 ml; the mass volume ratio of the washed and dried product to the anhydrous dimethyl sulfoxide solution is 1:30-40g/ml, wherein the content of the ascorbic acid/cyclodextrin inclusion compound in the anhydrous dimethyl sulfoxide solution is 10-18%, and the content of 4-dimethylaminopyridine is 3-6%; the washing is carried out for 5-6 times by adopting dried dichloromethane, acetone and methanol in turn; the drying temperature is 55-65 ℃, and the drying time is 10-13 h.
5. The rapidly degradable jelly packaging of claim 1, wherein in the preparing step 4), the vegetable starch is selected from at least one of corn starch, wheat starch, sweet potato starch, and siliconThe weight ratio of the sodium, the magnesium oxalate, the polylactic acid, the polyamide, the modified polymer microspheres and the sorbitol is 35-45:1-2:0.3-0.8:15-20:0.2-0.5:3-7: 5-9; the rotating speed of the high-speed mixer is 600-900 r/min; the double-screw extruder is divided into four temperature zones, namely a first zone of 140-; the temperature of the template compact is 160-165 ℃, and the pressure is 21-24Kg/cm
2And the compacting time is 3-6 min.
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| CN106220978A (en) * | 2016-07-21 | 2016-12-14 | 合肥市智源包装科技有限公司 | A kind of environment-friendly degradable type halloysite nanotubes polyethylene coating materials and preparation method thereof |
| CN108003579A (en) * | 2018-02-07 | 2018-05-08 | 东莞市绿睿塑胶科技有限公司 | A kind of environment-friendly degradable polybag and its manufacture craft |
| CN109370183A (en) * | 2018-10-26 | 2019-02-22 | 成都新柯力化工科技有限公司 | A kind of biological plastics and preparation method thereof being exclusively used in seawater degradation |
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Address after: 236500 Industrial Park, Fuyang City, Anhui Applicant after: Anhui Tianlu New Material Co.,Ltd. Address before: 236500 Industrial Park, Fuyang City, Anhui Applicant before: JIESHOU TIANLU PACKING MATERIAL Co.,Ltd. |
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Denomination of invention: A quick degradable jelly packaging shell Effective date of registration: 20220519 Granted publication date: 20220114 Pledgee: The development of small and medium-sized enterprises financing Company Limited by Guarantee Jieshou City Pledgor: Anhui Tianlu New Material Co.,Ltd. Registration number: Y2022980005800 |