CN112143187A - Antibacterial and mildew-proof degradable plastic and preparation method thereof - Google Patents

Antibacterial and mildew-proof degradable plastic and preparation method thereof Download PDF

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CN112143187A
CN112143187A CN202010956684.8A CN202010956684A CN112143187A CN 112143187 A CN112143187 A CN 112143187A CN 202010956684 A CN202010956684 A CN 202010956684A CN 112143187 A CN112143187 A CN 112143187A
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卢丽容
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • 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

Abstract

The invention belongs to the technical field of plastic processing, and particularly relates to an antibacterial mildew-proof degradable plastic and a preparation method thereof.

Description

Antibacterial and mildew-proof degradable plastic and preparation method thereof
Technical Field
The invention belongs to the technical field of plastic processing. More particularly, relates to an antibacterial mildew-proof degradable plastic and a preparation method thereof.
Background
Plastic products, especially film products, are in great demand in daily production and life. Common plastic products mainly comprise polyvinyl chloride raw materials, are difficult to degrade, have poor forming and processing performances, and need to be added with auxiliary agents such as pigments, plasticizers, anti-aging agents and the like during processing, and the chemicals are toxic and bring great harm to human beings and the environment during use. With the improvement of environmental awareness of people, biodegradable plastics enter the sight of people, contain active groups such as hydroxyl, ester, carboxyl and the like which are easily decomposed by microorganisms, and are easily decomposed into water and carbon dioxide under the action of the microorganisms and the like when being placed in a natural environment under certain temperature and humidity conditions, so that the biodegradable plastics return to the nature. Therefore, the treatment of the biodegradable plastic waste can adopt composting treatment, realize resource recycling and meet the requirement of sustainable development.
At present, biological polymers with biological degradation functions, such as polylactic acid (PLA), polybutylene succinate (PBS), carbon dioxide polymer (PPC), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA) and the like, are mainly synthesized by microbial fermentation or chemical synthesis of the biological degradable plastics. However, most of the currently developed fully biodegradable plastics have the cost of sacrificing mechanical performance indexes, and do not have market popularization value.
In addition, the plastic is easy to be infected with and breed various microorganisms in the using process, is easy to mildew and breed various pathogenic bacteria, and brings harm to the health of people. With the increasing health importance of people, more and more consumers want plastic products with antibacterial and mildewproof properties to reduce microbial contamination and cross infection of germs in daily life.
The existing antibacterial materials are mainly divided into three types: the first is natural antibacterial material, including chitin, chitosan and insect antibacterial protein extracted from animal, which has limited source, high selling price and less application in industrial products; the second type is an organic antibacterial and mildewproof material which mainly comprises quaternary ammonium salts, quaternary phosphonium salts, biguanides, alcohols, phenols, organic metals, pyridines, imidazoles and the like, and the organic antibacterial material has the greatest advantage of good antibacterial timeliness but has the problems of high toxicity, poor durability, drug resistance and the like; the third kind is inorganic antibiotic and mildew-proof material, which mainly comprises oxide photocatalysis material and metal ion metal oxide type, and has the advantages of antibiotic broad spectrum, long effect, no drug resistance, heat resistance, etc. At present, inorganic antibacterial materials containing metal ion types are widely applied, the main antibacterial metal ions are silver, copper and zinc, and the research and application of silver-carrying antibacterial agents are the most. However, the overall antibacterial timeliness of the inorganic antibacterial agent is weaker than that of the organic antibacterial material, and the silver antibacterial agent has the problems of easy color change, high cost and the like. The carrier materials used by the prior silver-carrying antibacterial material are mostly artificially synthesized zeolite, phosphate, silica gel, glass and the like, and the materials have the advantages of high purity, high whiteness, strong ion exchange capacity and the like, but have higher cost. From the analysis of three types of antibacterial materials, the existing single type antibacterial agent is difficult to meet the current market demand, and the broad-spectrum long-acting antibacterial and mildewproof effects are realized in the true sense.
Disclosure of Invention
The invention aims to solve the technical problems that the biodegradability and the mechanical property of the existing plastic product cannot be considered at the same time and the antibacterial and mildewproof effects are poor, and provides the antibacterial and mildewproof degradable plastic and the preparation method thereof.
The invention aims to provide a preparation method of an antibacterial mildew-proof degradable plastic.
The invention also aims to provide the antibacterial mildew-proof degradable plastic prepared by the preparation method.
The invention also aims to provide application of the antibacterial, mildewproof and degradable plastic as a packaging material.
The above purpose of the invention is realized by the following technical scheme:
1. a method for preparing antibacterial mildew-proof degradable plastics, obtain epoxidizing the product to dioxanone-caprolactone copolymer epoxidation first, then the ring-opening reaction of epoxidizing the product and modified nanometer filler gets the modified polymer, then mix the modified polymer with modified collagen to melt and extrude the tape casting, the said antibacterial mildew-proof degradable plastics of aftertreatment; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres;
(C) finally, dissolving polyhexamethylene guanidine phosphate in water, then adding the modified nanospheres, homogenizing under high pressure, and freeze-drying under vacuum to obtain the modified nano filler;
the modified collagen is obtained by blending collagen and dialdehyde starch.
Preferably, the preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 2-3 hours at 90-100 ℃, adding caprolactone, continuing to perform thermal insulation polymerization for 8-10 hours, dispersing the obtained reaction product in chloroform by using ultrasonic waves, adding methanol for precipitation, and drying to obtain the polymer.
Further preferably, the molar ratio of the dioxanone to the caprolactone is 1: 0.2-0.3, wherein the dosage of the stannous octoate toluene solution is 8-10% of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with the weight of 6-9 times of that of the stannous octoate.
Preferably, the epoxidation reaction is carried out by the following specific method: adding a dioxanone-caprolactone copolymer into formic acid, heating to 30-35 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 50-55 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 5-6 hours, and carrying out post-treatment to obtain an epoxidized product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.25-0.35: 0.1 to 0.2.
As a further preferable technical scheme, the dropping time of the hydrogen peroxide is 150-200 minutes.
As a further preferred technical solution, the post-treatment method specifically comprises: and (3) after the reaction is finished, washing the reaction product for 2-3 times with distilled water at the temperature of 50-55 ℃, and performing vacuum dehydration after the washing is finished.
Preferably, the preparation method of the modified polymer comprises the following steps in parts by weight: firstly, adding 1 part of epoxidation product and 0.08-0.1 part of modified nano filler into 5-7 parts of toluene, uniformly dispersing by ultrasonic waves, then adding 0.006-0.008 part of stannous octoate, stirring and reacting at 75-85 ℃ for 60-90 minutes, and removing the toluene by rotary evaporation to obtain the modified polymer.
Preferably, the specific method of mixing, melting, extruding and casting comprises the following steps in parts by weight: firstly, mixing 1 part of modified polymer and 0.2-0.3 part of modified collagen by using a mixer, then adding 0.001-0.002 part of phosphorus oxychloride, and carrying out melt extrusion casting at 120-130 ℃ by using an exhaust type double screw extruder to form a melt film.
Further preferably, the process parameters of the mixer are as follows: 1300-1500 r/min for 20-30 minutes.
Further preferably, the post-treatment method comprises the following specific steps: firstly, a molten film is cooled to form a film through a water tank filled with water of 10-20 ℃, then hot air drying is carried out at 80-90 ℃, and drying and shaping are carried out under the condition of tension.
Preferably, the preparation method of the modified collagen comprises the following steps in parts by weight: firstly premixing 1 part of collagen and 0.3-0.5 part of dialdehyde starch for 5-8 minutes by using a mixer, and then carrying out melt blending by using a single-screw extruder at the temperature of 50-70 ℃.
Preferably, the specific method of step (a) is as follows, in parts by weight: adding 1 part of ammonium molybdate into 5-8 parts of deionized water while stirring, adjusting the pH value to 8-9 by using 25-28% by mass of concentrated ammonia water, uniformly oscillating by ultrasonic waves, adding 0.6-0.8 part of selenium powder and 0.1-0.2 part of zinc powder, uniformly stirring, adding 9-10 parts of 50-60% by mass of hydrazine hydrate solution, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
Further preferably, the process conditions of the hydrothermal reaction are as follows: the reaction temperature is 220-240 ℃, and the reaction time is 18-22 hours.
Further preferably, the washing is carried out for 2-3 times by using deionized water and absolute ethyl alcohol alternately; the drying process conditions are as follows: vacuum drying at 70-80 ℃ for 8-10 hours.
Preferably, the specific method of step (B) is: adding zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane in an amount which is 5-8 times the weight of the zinc-doped molybdenum selenide nanospheres, uniformly dispersing by ultrasonic waves, heating at 110-120 ℃ for 3-4 hours, and centrifuging to obtain precipitates, thus obtaining the modified nanospheres.
Preferably, in the step (C), the mass ratio of the polyhexamethylene guanidine phosphate to the water to the modified nanospheres is 1: 5-8: 2 to 3.
Preferably, in the step (C), the process conditions of high-pressure homogenization are as follows: 400 to 500Pa for 3 to 5 times.
Preferably, in step (C), the vacuum freeze-drying process conditions are as follows: cooling to-40 to-50 ℃, preserving heat for 8 to 10 hours, then vacuumizing to 2 to 3Pa, keeping the vacuum degree, heating to 20 to 30 ℃, and preserving heat for 5 to 7 hours.
2. The antibacterial mildew-proof degradable plastic is obtained by the preparation method.
3. The antibacterial and mildewproof degradable plastic is applied as a packaging material.
Preferably, the packaging material is a food or pharmaceutical packaging material.
The invention has the following beneficial effects:
the invention firstly performs epoxidation reaction on dioxanone-caprolactone copolymer to obtain an epoxidized product, then performs ring-opening reaction on the epoxidized product and modified nano filler to obtain a modified polymer, then mixes the modified polymer and modified collagen for melting, extruding and casting, and performs post-treatment to obtain the antibacterial mildew-proof degradable plastic which is biodegradable, has good mechanical property, takes the biodegradability and the mechanical property of plastic products into account, and has good antibacterial mildew-proof effect. The specific analysis is as follows:
1. the main raw materials of the invention are the dioxanone-caprolactone copolymer and the modified collagen, both of which have good biodegradability, and the hydroxyl in the dioxanone-caprolactone copolymer and the hydroxyl, amino and the like contained in the modified collagen form hydrogen bond action, and the formation of the hydrogen bond action constructs a net structure, thereby enhancing the mechanical property, and the invention also has certain surface barrier property, avoids the breeding of bacteria and mould and has certain antibacterial and mildewproof effects.
The modified collagen is obtained by blending collagen and dialdehyde starch, and aldehyde functional groups of the dialdehyde starch react with the collagen, so that the collagen is esterified, the mechanical property of the obtained modified collagen is improved, meanwhile, the collagen is prevented from becoming a nutrient source of bacteria and mould, and the antibacterial and mildewproof effects are further enhanced.
2. The key technology of the invention is that the modified nano-filler is prepared by taking ammonium molybdate, selenium powder and zinc powder as raw materials and preparing zinc-doped molybdenum selenide nanospheres through hydrothermal reaction; then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres; and finally, dissolving the polyhexamethylene guanidine phosphate in water, adding the modified nanospheres, homogenizing under high pressure, and carrying out vacuum freeze drying to obtain the compound.
In the zinc-doped molybdenum selenide nanospheres, metal molybdenum, zinc and the like have a certain sterilization effect, and selenium has an electron-withdrawing effect on zinc, so that zinc is ionized and forms complex ions with protein, and the function of the protein is lost, thereby playing an antibacterial and mildewproof role. The zinc-doped molybdenum selenide nanospheres are modified by N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, amino is introduced, polyhexamethylene guanidine phosphate (with antibacterial activity) contains a large amount of hydroxyl, amino and the like, hydrogen bonds can be formed among the hydroxyl, amino and the like, and a net structure is constructed by the formation of the hydrogen bond action, so that the mechanical property is further enhanced, the surface barrier property is enhanced, and the antibacterial and mildewproof effects are further enhanced.
Most importantly, amino groups in the modified nano filler can form covalent bonds with an epoxidation product through a ring-opening reaction, so that the filler component exists in a system in the form of chemical bonds, and compared with simple physical mixing, the modified nano filler has better dispersibility and stability in the system, and ensures the mechanical properties and the antibacterial and mildewproof effects of the product.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A method for preparing antibacterial mildew-proof degradable plastics, obtain epoxidizing the product to dioxanone-caprolactone copolymer epoxidation first, then the ring-opening reaction of epoxidizing the product and modified nanometer filler gets the modified polymer, then mix the modified polymer with modified collagen to melt and extrude the tape casting, the said antibacterial mildew-proof degradable plastics of aftertreatment; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres;
(C) finally, dissolving polyhexamethylene guanidine phosphate in water, then adding the modified nanospheres, homogenizing under high pressure, and freeze-drying under vacuum to obtain the modified nano filler;
the modified collagen is obtained by blending collagen and dialdehyde starch.
The preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 3 hours at 90 ℃, adding caprolactone, continuing to perform heat preservation polymerization for 8 hours, ultrasonically dispersing the obtained reaction product in chloroform, adding methanol for precipitation, and drying to obtain the polymer.
The molar ratio of the dioxanone to the caprolactone is 1: 0.3, the dosage of the stannous octoate toluene solution is 8 percent of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with the weight being 9 times that of the solution.
The specific method of the epoxidation reaction is as follows: adding the dioxanone-caprolactone copolymer into formic acid, heating to 30 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 55 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 5 hours, and carrying out post-treatment to obtain an epoxidation product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.35: 0.1.
the dropping time of the hydrogen peroxide is 200 minutes.
The specific method of post-treatment is as follows: and after the reaction is finished, washing the mixture for 3 times by using distilled water at 50 ℃ while the mixture is hot, and performing vacuum dehydration after the washing is finished.
The preparation method of the modified polymer comprises the following steps: firstly, adding 1kg of epoxidation product and 0.08kg of modified nano filler into 7kg of toluene, uniformly dispersing by ultrasonic waves, then adding 0.006kg of stannous octoate, stirring and reacting for 60 minutes at 85 ℃, and removing the toluene by rotary evaporation to obtain the modified polymer.
The specific method of mixing, melting, extruding and casting comprises the following steps: firstly, mixing 1kg of modified polymer and 0.3kg of modified collagen by a mixer, then adding 0.001kg of phosphorus oxychloride, and carrying out melt extrusion and tape casting by adopting an exhaust type double-screw extruder at the temperature of 130 ℃ to form a melt film.
The technological parameters of the mixer are as follows: 1300r/min for 30 minutes.
The specific method of post-treatment is as follows: the melt film is cooled to form a film through a water tank filled with water of 10 ℃, then the film is dried by hot air of 90 ℃, and the film is dried and shaped under the condition of tension.
The preparation method of the modified collagen comprises the following steps: 1kg of collagen and 0.3kg of dialdehyde starch are premixed for 8 minutes by a mixer and then melted and blended by a single screw extruder at the temperature of 50 ℃.
The specific method of the step (A) is as follows: adding 1kg of ammonium molybdate into 8kg of deionized water while stirring, adjusting the pH value to 9 by using 25% concentrated ammonia water by mass, uniformly oscillating by ultrasonic waves, adding 0.6kg of selenium powder and 0.2kg of zinc powder, uniformly stirring, adding 9kg of 60% hydrazine hydrate solution by mass, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
The technological conditions of the hydrothermal reaction are as follows: the reaction temperature was 220 ℃ and the reaction time was 22 hours.
Alternately washing for 2 times by using deionized water and absolute ethyl alcohol; the drying process conditions are as follows: vacuum drying at 80 deg.C for 8 hr.
The specific method of the step (B) is as follows: adding the zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane with the weight of 8 times, uniformly dispersing by ultrasonic waves, heating at 110 ℃ for 4 hours, and centrifuging to obtain precipitates, thus obtaining the modified nanospheres.
In the step (C), the mass ratio of the polyhexamethylene guanidine phosphate to the water to the modified nanospheres is 1: 5: 3.
in the step (C), the process conditions of high-pressure homogenization are as follows: 400Pa treatment 5 times.
In the step (C), the process conditions of vacuum freeze drying are as follows: cooling to-40 deg.C, maintaining the temperature for 10 hr, vacuumizing to 2Pa, maintaining the vacuum degree, heating to 30 deg.C, and maintaining the temperature for 5 hr.
Example 2
A method for preparing antibacterial mildew-proof degradable plastics, obtain epoxidizing the product to dioxanone-caprolactone copolymer epoxidation first, then the ring-opening reaction of epoxidizing the product and modified nanometer filler gets the modified polymer, then mix the modified polymer with modified collagen to melt and extrude the tape casting, the said antibacterial mildew-proof degradable plastics of aftertreatment; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres;
(C) finally, dissolving polyhexamethylene guanidine phosphate in water, then adding the modified nanospheres, homogenizing under high pressure, and freeze-drying under vacuum to obtain the modified nano filler;
the modified collagen is obtained by blending collagen and dialdehyde starch.
The preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 2 hours at 100 ℃, adding caprolactone, continuing to perform heat preservation polymerization for 10 hours, ultrasonically dispersing the obtained reaction product in chloroform, adding methanol for precipitation, and drying to obtain the polymer.
The molar ratio of the dioxanone to the caprolactone is 1: 0.2, the dosage of the stannous octoate toluene solution is 10 percent of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with 6 times of the weight of the stannous octoate.
The specific method of the epoxidation reaction is as follows: adding the dioxanone-caprolactone copolymer into formic acid, heating to 35 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 50 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 6 hours, and carrying out post-treatment to obtain an epoxidation product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.25: 0.2.
the dropping time of the hydrogen peroxide is 150 minutes.
The specific method of post-treatment is as follows: and after the reaction is finished, washing the mixture for 2 times by using distilled water at 55 ℃ while the mixture is hot, and performing vacuum dehydration after the washing is finished.
The preparation method of the modified polymer comprises the following steps: firstly, adding 1kg of epoxidation product and 0.1kg of modified nano filler into 5kg of toluene, uniformly dispersing by ultrasonic waves, then adding 0.008kg of stannous octoate, stirring and reacting for 90 minutes at 75 ℃, and removing the toluene by rotary evaporation to obtain the modified polymer.
The specific method of mixing, melting, extruding and casting comprises the following steps: firstly, mixing 1kg of modified polymer and 0.2kg of modified collagen by a mixer, then adding 0.002kg of phosphorus oxychloride, and carrying out melt extrusion and tape casting by adopting an exhaust type double-screw extruder at the temperature of 120 ℃ to form a melt film.
The technological parameters of the mixer are as follows: mixing at 1500r/min for 20 min.
The specific method of post-treatment is as follows: firstly, the molten film is cooled to form a film through a water tank filled with water of 20 ℃, then the film is dried by hot air of 80 ℃, and drying and shaping are carried out under the condition of tension.
The preparation method of the modified collagen comprises the following steps: 1kg of collagen and 0.5kg of dialdehyde starch are premixed for 5 minutes by a mixer and then melted and blended by a single screw extruder at the temperature of 70 ℃.
The specific method of the step (A) is as follows: adding 1kg of ammonium molybdate into 5kg of deionized water while stirring, adjusting the pH value to 8 by using concentrated ammonia water with the mass concentration of 28%, uniformly oscillating by ultrasonic waves, adding 0.8kg of selenium powder and 0.1kg of zinc powder, uniformly stirring, adding 10kg of hydrazine hydrate solution with the mass concentration of 50%, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
The technological conditions of the hydrothermal reaction are as follows: the reaction temperature was 240 ℃ and the reaction time was 18 hours.
Alternately washing for 3 times by using deionized water and absolute ethyl alcohol; the drying process conditions are as follows: vacuum drying at 70 deg.C for 10 hr.
The specific method of the step (B) is as follows: adding the zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane with the weight of 5 times, uniformly dispersing by ultrasonic waves, heating at 120 ℃ for 3 hours, and centrifuging to obtain precipitates, thus obtaining the modified nanospheres.
In the step (C), the mass ratio of the polyhexamethylene guanidine phosphate to the water to the modified nanospheres is 1: 8: 2.
in the step (C), the process conditions of high-pressure homogenization are as follows: 500Pa treatment 3 times.
In the step (C), the process conditions of vacuum freeze drying are as follows: cooling to-50 deg.C, maintaining the temperature for 8 hr, vacuumizing to 3Pa, maintaining the vacuum degree, heating to 20 deg.C, and maintaining the temperature for 7 hr.
Example 3
A method for preparing antibacterial mildew-proof degradable plastics, obtain epoxidizing the product to dioxanone-caprolactone copolymer epoxidation first, then the ring-opening reaction of epoxidizing the product and modified nanometer filler gets the modified polymer, then mix the modified polymer with modified collagen to melt and extrude the tape casting, the said antibacterial mildew-proof degradable plastics of aftertreatment; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres;
(C) finally, dissolving polyhexamethylene guanidine phosphate in water, then adding the modified nanospheres, homogenizing under high pressure, and freeze-drying under vacuum to obtain the modified nano filler;
the modified collagen is obtained by blending collagen and dialdehyde starch.
The preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 2.5 hours at 95 ℃, adding caprolactone, continuing to perform heat preservation polymerization for 9 hours, ultrasonically dispersing the obtained reaction product in chloroform, adding methanol for precipitation, and drying to obtain the polymer.
The molar ratio of the dioxanone to the caprolactone is 1: 0.25, the dosage of the stannous octoate toluene solution is 9 percent of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with the weight being 8 times that of the solution.
The specific method of the epoxidation reaction is as follows: firstly, adding the dioxanone-caprolactone copolymer into formic acid, heating to 32 ℃, then slowly dripping hydrogen peroxide while stirring, heating to 53 ℃ after the dripping of the hydrogen peroxide is finished, carrying out heat preservation reaction for 5.5 hours, and carrying out post-treatment to obtain an epoxidation product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.3: 0.15.
the dropping time of the hydrogen peroxide is 180 minutes.
The specific method of post-treatment is as follows: after the reaction is finished, the mixture is washed for 2 times by distilled water with the temperature of 52 ℃ while the mixture is hot, and the mixture is dehydrated in vacuum after the washing is finished.
The preparation method of the modified polymer comprises the following steps: firstly, adding 1kg of epoxidation product and 0.09kg of modified nano filler into 6kg of toluene, uniformly dispersing by ultrasonic waves, then adding 0.007kg of stannous octoate, stirring and reacting for 75 minutes at 80 ℃, and removing the toluene by rotary evaporation to obtain the modified polymer.
The specific method of mixing, melting, extruding and casting comprises the following steps: firstly, mixing 1kg of modified polymer and 0.25kg of modified collagen by a mixer, then adding 0.0015kg of phosphorus oxychloride, and carrying out melt extrusion and tape casting by adopting an exhaust type double-screw extruder at 125 ℃ to form a melt film.
The technological parameters of the mixer are as follows: mix at 1400r/min for 25 minutes.
The specific method of post-treatment is as follows: the melt film is cooled to form a film through a water tank filled with 15 ℃ water, and then the film is dried by hot air at 85 ℃ and is dried and shaped under the condition of tension.
The preparation method of the modified collagen comprises the following steps: 1kg of collagen and 0.4kg of dialdehyde starch are premixed for 7 minutes by a mixer and then melted and blended by a single screw extruder at the temperature of 60 ℃.
The specific method of the step (A) is as follows: adding 1kg of ammonium molybdate into 7kg of deionized water while stirring, adjusting the pH value to 8 by using 27% concentrated ammonia water by mass, uniformly oscillating by ultrasonic waves, adding 0.7kg of selenium powder and 0.15kg of zinc powder, uniformly stirring, adding 9.5kg of 55% hydrazine hydrate solution by mass, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
The technological conditions of the hydrothermal reaction are as follows: the reaction temperature is 230 ℃, and the reaction time is 20 hours.
Alternately washing for 3 times by using deionized water and absolute ethyl alcohol; the drying process conditions are as follows: vacuum drying at 75 deg.C for 9 hr.
The specific method of the step (B) is as follows: adding the zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane with the weight of 6 times, uniformly dispersing by ultrasonic waves, heating at 115 ℃ for 3.5 hours, and centrifuging to obtain precipitates, thus obtaining the modified nanospheres.
In the step (C), the mass ratio of the polyhexamethylene guanidine phosphate to the water to the modified nanospheres is 1: 6: 2.5.
in the step (C), the process conditions of high-pressure homogenization are as follows: the treatment was carried out 4 times at 500 Pa.
In the step (C), the process conditions of vacuum freeze drying are as follows: cooling to-45 deg.C, maintaining for 9 hr, vacuumizing to 2Pa, maintaining vacuum degree, heating to 25 deg.C, and maintaining for 6 hr.
Comparative example 1
A method for preparing antibacterial mildew-proof degradable plastics, firstly, carrying out epoxidation reaction on dioxanone-caprolactone copolymer to obtain an epoxidized product, then carrying out ring-opening reaction on the epoxidized product and modified nano filler to obtain a modified polymer, then carrying out melt extrusion casting on the modified polymer, and carrying out post-treatment to obtain the antibacterial mildew-proof degradable plastics; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres;
(C) and finally, dissolving polyhexamethylene guanidine phosphate in water, adding the modified nanospheres, homogenizing under high pressure, and freeze-drying in vacuum to obtain the modified nano filler.
The preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 3 hours at 90 ℃, adding caprolactone, continuing to perform heat preservation polymerization for 8 hours, ultrasonically dispersing the obtained reaction product in chloroform, adding methanol for precipitation, and drying to obtain the polymer.
The molar ratio of the dioxanone to the caprolactone is 1: 0.3, the dosage of the stannous octoate toluene solution is 8 percent of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with the weight being 9 times that of the solution.
The specific method of the epoxidation reaction is as follows: adding the dioxanone-caprolactone copolymer into formic acid, heating to 30 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 55 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 5 hours, and carrying out post-treatment to obtain an epoxidation product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.35: 0.1.
the dropping time of the hydrogen peroxide is 200 minutes.
The specific method of post-treatment is as follows: and after the reaction is finished, washing the mixture for 3 times by using distilled water at 50 ℃ while the mixture is hot, and performing vacuum dehydration after the washing is finished.
The preparation method of the modified polymer comprises the following steps: firstly, adding 1kg of epoxidation product and 0.08kg of modified nano filler into 7kg of toluene, uniformly dispersing by ultrasonic waves, then adding 0.006kg of stannous octoate, stirring and reacting for 60 minutes at 85 ℃, and removing the toluene by rotary evaporation to obtain the modified polymer.
The specific method of melt extrusion casting is as follows: firstly, mixing 1kg of modified polymer and 0.001kg of phosphorus oxychloride by using a mixer, and then carrying out melt extrusion and tape casting by using an exhaust type double-screw extruder at the temperature of 130 ℃ to form a melt film.
The technological parameters of the mixer are as follows: 1300r/min for 30 minutes.
The specific method of post-treatment is as follows: the melt film is cooled to form a film through a water tank filled with water of 10 ℃, then the film is dried by hot air of 90 ℃, and the film is dried and shaped under the condition of tension.
The specific method of the step (A) is as follows: adding 1kg of ammonium molybdate into 8kg of deionized water while stirring, adjusting the pH value to 9 by using 25% concentrated ammonia water by mass, uniformly oscillating by ultrasonic waves, adding 0.6kg of selenium powder and 0.2kg of zinc powder, uniformly stirring, adding 9kg of 60% hydrazine hydrate solution by mass, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
The technological conditions of the hydrothermal reaction are as follows: the reaction temperature was 220 ℃ and the reaction time was 22 hours.
Alternately washing for 2 times by using deionized water and absolute ethyl alcohol; the drying process conditions are as follows: vacuum drying at 80 deg.C for 8 hr.
The specific method of the step (B) is as follows: adding the zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane with the weight of 8 times, uniformly dispersing by ultrasonic waves, heating at 110 ℃ for 4 hours, and centrifuging to obtain precipitates, thus obtaining the modified nanospheres.
In the step (C), the mass ratio of the polyhexamethylene guanidine phosphate to the water to the modified nanospheres is 1: 5: 3.
in the step (C), the process conditions of high-pressure homogenization are as follows: 400Pa treatment 5 times.
In the step (C), the process conditions of vacuum freeze drying are as follows: cooling to-40 deg.C, maintaining the temperature for 10 hr, vacuumizing to 2Pa, maintaining the vacuum degree, heating to 30 deg.C, and maintaining the temperature for 5 hr.
Comparative example 2
A method for preparing antibacterial mildew-proof degradable plastics, obtain epoxidizing the product to dioxanone-caprolactone copolymer epoxidation first, then the ring-opening reaction of epoxidizing the product and modified nanometer filler gets the modified polymer, then mix the modified polymer with modified collagen to melt and extrude the tape casting, the said antibacterial mildew-proof degradable plastics of aftertreatment; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then, dissolving polyhexamethylene guanidine phosphate in water, adding zinc-doped molybdenum selenide nanospheres, homogenizing under high pressure, and freeze-drying in vacuum to obtain the modified nano filler;
the modified collagen is obtained by blending collagen and dialdehyde starch.
The preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 3 hours at 90 ℃, adding caprolactone, continuing to perform heat preservation polymerization for 8 hours, ultrasonically dispersing the obtained reaction product in chloroform, adding methanol for precipitation, and drying to obtain the polymer.
The molar ratio of the dioxanone to the caprolactone is 1: 0.3, the dosage of the stannous octoate toluene solution is 8 percent of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with the weight being 9 times that of the solution.
The specific method of the epoxidation reaction is as follows: adding the dioxanone-caprolactone copolymer into formic acid, heating to 30 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 55 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 5 hours, and carrying out post-treatment to obtain an epoxidation product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.35: 0.1.
the dropping time of the hydrogen peroxide is 200 minutes.
The specific method of post-treatment is as follows: and after the reaction is finished, washing the mixture for 3 times by using distilled water at 50 ℃ while the mixture is hot, and performing vacuum dehydration after the washing is finished.
The preparation method of the modified polymer comprises the following steps: firstly, adding 1kg of epoxidation product and 0.08kg of modified nano filler into 7kg of toluene, uniformly dispersing by ultrasonic waves, then adding 0.006kg of stannous octoate, stirring and reacting for 60 minutes at 85 ℃, and removing the toluene by rotary evaporation to obtain the modified polymer.
The specific method of mixing, melting, extruding and casting comprises the following steps: firstly, mixing 1kg of modified polymer and 0.3kg of modified collagen by a mixer, then adding 0.001kg of phosphorus oxychloride, and carrying out melt extrusion and tape casting by adopting an exhaust type double-screw extruder at the temperature of 130 ℃ to form a melt film.
The technological parameters of the mixer are as follows: 1300r/min for 30 minutes.
The specific method of post-treatment is as follows: the melt film is cooled to form a film through a water tank filled with water of 10 ℃, then the film is dried by hot air of 90 ℃, and the film is dried and shaped under the condition of tension.
The preparation method of the modified collagen comprises the following steps: 1kg of collagen and 0.3kg of dialdehyde starch are premixed for 8 minutes by a mixer and then melted and blended by a single screw extruder at the temperature of 50 ℃.
The specific method of the step (A) is as follows: adding 1kg of ammonium molybdate into 8kg of deionized water while stirring, adjusting the pH value to 9 by using 25% concentrated ammonia water by mass, uniformly oscillating by ultrasonic waves, adding 0.6kg of selenium powder and 0.2kg of zinc powder, uniformly stirring, adding 9kg of 60% hydrazine hydrate solution by mass, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
The technological conditions of the hydrothermal reaction are as follows: the reaction temperature was 220 ℃ and the reaction time was 22 hours.
Alternately washing for 2 times by using deionized water and absolute ethyl alcohol; the drying process conditions are as follows: vacuum drying at 80 deg.C for 8 hr.
In the step (B), the mass ratio of the polyhexamethylene guanidine phosphate to the water to the zinc doped molybdenum selenide nanospheres is 1: 5: 3.
in the step (B), the process conditions of high-pressure homogenization are as follows: 400Pa treatment 5 times.
In the step (B), the process conditions of vacuum freeze drying are as follows: cooling to-40 deg.C, maintaining the temperature for 10 hr, vacuumizing to 2Pa, maintaining the vacuum degree, heating to 30 deg.C, and maintaining the temperature for 5 hr.
Comparative example 3
A method for preparing antibacterial mildew-proof degradable plastics, obtain epoxidizing the product to dioxanone-caprolactone copolymer epoxidation first, then the ring-opening reaction of epoxidizing the product and modified nanometer filler gets the modified polymer, then mix the modified polymer with modified collagen to melt and extrude the tape casting, the said antibacterial mildew-proof degradable plastics of aftertreatment; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain the modified nanofiller;
the modified collagen is obtained by blending collagen and dialdehyde starch.
The preparation method of the p-dioxanone-caprolactone copolymer comprises the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 3 hours at 90 ℃, adding caprolactone, continuing to perform heat preservation polymerization for 8 hours, ultrasonically dispersing the obtained reaction product in chloroform, adding methanol for precipitation, and drying to obtain the polymer.
The molar ratio of the dioxanone to the caprolactone is 1: 0.3, the dosage of the stannous octoate toluene solution is 8 percent of the weight of the dioxanone, and the stannous octoate toluene solution is obtained by dissolving stannous octoate in toluene with the weight being 9 times that of the solution.
The specific method of the epoxidation reaction is as follows: adding the dioxanone-caprolactone copolymer into formic acid, heating to 30 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 55 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 5 hours, and carrying out post-treatment to obtain an epoxidation product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.35: 0.1.
the dropping time of the hydrogen peroxide is 200 minutes.
The specific method of post-treatment is as follows: and after the reaction is finished, washing the mixture for 3 times by using distilled water at 50 ℃ while the mixture is hot, and performing vacuum dehydration after the washing is finished.
The preparation method of the modified polymer comprises the following steps: firstly, adding 1kg of epoxidation product and 0.08kg of modified nano filler into 7kg of toluene, uniformly dispersing by ultrasonic waves, then adding 0.006kg of stannous octoate, stirring and reacting for 60 minutes at 85 ℃, and removing the toluene by rotary evaporation to obtain the modified polymer.
The specific method of mixing, melting, extruding and casting comprises the following steps: firstly, mixing 1kg of modified polymer and 0.3kg of modified collagen by a mixer, then adding 0.001kg of phosphorus oxychloride, and carrying out melt extrusion and tape casting by adopting an exhaust type double-screw extruder at the temperature of 130 ℃ to form a melt film.
The technological parameters of the mixer are as follows: 1300r/min for 30 minutes.
The specific method of post-treatment is as follows: the melt film is cooled to form a film through a water tank filled with water of 10 ℃, then the film is dried by hot air of 90 ℃, and the film is dried and shaped under the condition of tension.
The preparation method of the modified collagen comprises the following steps: 1kg of collagen and 0.3kg of dialdehyde starch are premixed for 8 minutes by a mixer and then melted and blended by a single screw extruder at the temperature of 50 ℃.
The specific method of the step (A) is as follows: adding 1kg of ammonium molybdate into 8kg of deionized water while stirring, adjusting the pH value to 9 by using 25% concentrated ammonia water by mass, uniformly oscillating by ultrasonic waves, adding 0.6kg of selenium powder and 0.2kg of zinc powder, uniformly stirring, adding 9kg of 60% hydrazine hydrate solution by mass, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature (25 ℃), filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
The technological conditions of the hydrothermal reaction are as follows: the reaction temperature was 220 ℃ and the reaction time was 22 hours.
Alternately washing for 2 times by using deionized water and absolute ethyl alcohol; the drying process conditions are as follows: vacuum drying at 80 deg.C for 8 hr.
The specific method of the step (B) is as follows: adding the zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane with the weight of 8 times, uniformly dispersing by ultrasonic waves, heating at 110 ℃ for 4 hours, and centrifuging to obtain the precipitate.
Test examples
1. Investigation of biodegradability
Respectively burying the plastic products with the same weight in natural environment soil (soil pit of farmland 100cm multiplied by 100 cm), sampling at regular time and recording the mass loss, namely the degradation rate, the degradation rate＝(m0-mt)/m0X 100%, wherein m0As initial mass, mtThe results are shown in Table 1 for the residual mass after t months of degradation.
TABLE 1 biodegradability examination
Degradation rate (%, t ═ 1) Degradation rate (%, t ═ 3)
Example 1 40.1 100
Example 2 40.3 100
Example 3 40.8 100
As is clear from Table 1, the plastics obtained in examples 1 to 3 had good biodegradability.
2. Investigation of mechanical properties and antibacterial and mildewproof effects
The plastic products obtained in examples 1-3 and comparative examples 1-3 were respectively tested for mechanical properties and antibacterial and antifungal effects, and the results are shown in tables 2 and 3.
The detection of tensile strength and elongation at break is referred to GB/T1040.1-2018.
The antibacterial performance is referred to QB/T2591-2003, and the mildew-proof performance is referred to GB/T24128-2009.
TABLE 2 investigation of mechanical Properties
Tensile Strength (MPa) Elongation at Break (%)
Example 1 35.9 395
Example 2 35.3 393
Example 3 36.3 402
Comparative example 1 30.1 356
Comparative example 2 31.2 369
Comparative example 3 30.8 361
TABLE 3 investigation of antibacterial and antimildew Properties
Figure BDA0002678870990000161
As can be seen from tables 2 and 3, the plastics obtained in examples 1 to 3 had good mechanical properties and antibacterial and antifungal effects.
Comparative example 1 omits the modified collagen, has influenced the formation of the network structure, the mechanical property and antibacterial mildew-proof effect of the product are obviously worsened; the nano filler of the comparative example 2 is not modified, so that the nano filler has poor dispersibility in a system, and the mechanical property and the antibacterial and mildewproof effects of the product are influenced; comparative example 3 in the preparation of modified nano filler omitting poly hexamethylene guanidine phosphate, influence with nanosphere synergistic antibacterial mildew-proof function, product mechanical properties and antibacterial mildew-proof effect obviously worsen.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of an antibacterial mildew-proof degradable plastic is characterized in that a dioxanone-caprolactone copolymer is subjected to epoxidation reaction to obtain an epoxidation product, the epoxidation product is subjected to ring-opening reaction with a modified nano filler to obtain a modified polymer, the modified polymer and modified collagen are mixed, melted, extruded and cast, and post-treated to obtain the antibacterial mildew-proof degradable plastic; wherein the modified nano filler is prepared by the following method:
(A) firstly, preparing zinc-doped molybdenum selenide nanospheres by taking ammonium molybdate, selenium powder and zinc powder as raw materials through a hydrothermal reaction;
(B) then modifying the zinc-doped molybdenum selenide nanospheres by using N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to obtain modified nanospheres;
(C) finally, dissolving polyhexamethylene guanidine phosphate in water, then adding the modified nanospheres, homogenizing under high pressure, and freeze-drying under vacuum to obtain the modified nano filler;
the modified collagen is obtained by blending collagen and dialdehyde starch.
2. The method according to claim 1, wherein the p-dioxanone-caprolactone copolymer is prepared by the following steps: vacuumizing a strictly dried polymerization reaction kettle, introducing nitrogen for three times, sequentially injecting p-dioxanone and stannous octoate toluene solution by using a dried injector, polymerizing for 2-3 hours at 90-100 ℃, adding caprolactone, continuing to perform thermal insulation polymerization for 8-10 hours, dispersing the obtained reaction product in chloroform by using ultrasonic waves, adding methanol for precipitation, and drying to obtain the polymer.
3. The method according to claim 1, wherein the epoxidation reaction is carried out by a specific method comprising: adding a dioxanone-caprolactone copolymer into formic acid, heating to 30-35 ℃, then slowly dropwise adding hydrogen peroxide while stirring, heating to 50-55 ℃ after dropwise adding the hydrogen peroxide, carrying out heat preservation reaction for 5-6 hours, and carrying out post-treatment to obtain an epoxidized product; wherein the mass ratio of the dioxanone-caprolactone copolymer to the formic acid to the hydrogen peroxide is 1: 0.25-0.35: 0.1 to 0.2.
4. The method according to claim 1, wherein the modified polymer is prepared by the following method in parts by weight: firstly, adding 1 part of epoxidation product and 0.08-0.1 part of modified nano filler into 5-7 parts of toluene, uniformly dispersing by ultrasonic waves, then adding 0.006-0.008 part of stannous octoate, stirring and reacting at 75-85 ℃ for 60-90 minutes, and removing the toluene by rotary evaporation to obtain the modified polymer.
5. The production method according to claim 1, characterized in that a specific method of the mixing melt extrusion casting is, in parts by weight: firstly, mixing 1 part of modified polymer and 0.2-0.3 part of modified collagen by using a mixer, then adding 0.001-0.002 part of phosphorus oxychloride, and carrying out melt extrusion casting at 120-130 ℃ by using an exhaust type double screw extruder to form a melt film.
6. The method according to claim 1, wherein the modified collagen is prepared by the following steps in parts by weight: firstly premixing 1 part of collagen and 0.3-0.5 part of dialdehyde starch for 5-8 minutes by using a mixer, and then carrying out melt blending by using a single-screw extruder at the temperature of 50-70 ℃.
7. The preparation method according to claim 1, wherein the specific method of step (a) is as follows, in parts by weight: adding 1 part of ammonium molybdate into 5-8 parts of deionized water while stirring, adjusting the pH value to 8-9 by using 25-28% by mass of concentrated ammonia water, uniformly oscillating by ultrasonic waves, adding 0.6-0.8 part of selenium powder and 0.1-0.2 part of zinc powder, uniformly stirring, adding 9-10 parts of 50-60% by mass of hydrazine hydrate solution, and uniformly oscillating by ultrasonic waves to obtain premixed slurry; then transferring the premixed slurry into a hydrothermal reaction kettle for hydrothermal reaction; and after the hydrothermal reaction is finished, naturally cooling to room temperature, filtering, washing and drying to obtain the zinc-doped molybdenum selenide nanospheres.
8. The method according to claim 1, wherein the step (B) is carried out by a specific method comprising: adding zinc-doped molybdenum selenide nanospheres into N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane in an amount which is 5-8 times the weight of the zinc-doped molybdenum selenide nanospheres, uniformly dispersing by ultrasonic waves, heating at 110-120 ℃ for 3-4 hours, and centrifuging to obtain precipitates, thus obtaining the modified nanospheres.
9. An antibacterial and mildewproof degradable plastic obtained by the preparation method of any one of claims 1 to 8.
10. Use of the antibacterial, mildewproof and degradable plastic as claimed in claim 9 as a packaging material.
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