CN116218173A - New packaging bag material with strong antibacterial property and preparation method thereof - Google Patents
New packaging bag material with strong antibacterial property and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0806—Silver
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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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
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- 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 application relates to the field of high polymer materials, and particularly discloses a novel packaging bag material with strong antibacterial property and a preparation method thereof. The novel packaging bag material with strong antibacterial property comprises the following components in parts by weight: 60-90 parts of polyhydroxyalkanoate, 20-30 parts of polypropylene carbonate, 0.5-1 part of zinc acetate, 3-6 parts of plasticizer, 5-15 parts of antibacterial master batch, 1-4 parts of antioxidant and 0.8-3.2 parts of degradation accelerator; the antibacterial master batch comprises: 2-6 parts of starch, 1-3 parts of polyvinyl alcohol, 0.1-0.3 part of nano titanium dioxide, 0.2-0.5 part of nano silicon dioxide, 0.25-0.5 part of soluble rare earth salt, 0.05-0.1 part of silane coupling agent and 1-3 parts of loofah sponge fiber. The novel packaging bag material with strong antibacterial property has the advantages of strong antibacterial property, biodegradability, high degradation speed, good barrier property and excellent fresh-keeping effect.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a novel packaging bag material with strong antibacterial property and a preparation method thereof.
Background
Plastic packages and plastic packaging products have a larger and larger share in the market, particularly composite plastic flexible packages, have been widely applied to the fields of food, medicine, chemical industry and the like, wherein the plastic packaging film is one of the most widely used materials in plastic packages, such as beverage packages, quick-frozen food packages, steamed food packages, snack food packages and the like, which bring great convenience to life.
At present, the plastic is widely applied to food packaging materials, and the polyethylene film has no odor, no toxicity, good moisture absorption resistance and good solvent resistance and chemical stability, so that the polyethylene film is used as the packaging material and is widely applied to the fields of food transportation, food packaging, daily necessities packaging and the like.
In the prior art, the application document of Chinese invention patent application No. 2020116067647 discloses a polyethylene material for food packaging bags, which comprises the following raw materials in parts by weight: 80-100 parts of polyethylene, 10-20 parts of impact modifier, 8-10 parts of filler, 0.1-0.3 part of stearic acid and 2-3 parts of compatilizer, wherein the filler is talcum powder, organized nano montmorillonite and modified graphene.
In view of the above-mentioned related art, the inventors found that the present polyethylene material has excellent mechanical properties, but the antibacterial properties are poor, and polyethylene is hardly degraded, which is very polluting the environment.
Disclosure of Invention
In order to improve the antibacterial performance of food packaging bag materials and enable packaging bags to be easily degraded, the application provides a novel packaging bag material with strong antibacterial performance and a preparation method thereof.
In a first aspect, the present application provides a new packaging bag material with strong antibacterial property, and adopts the following technical scheme: a novel packaging bag material with strong antibacterial property comprises the following components in parts by weight: 60-90 parts of polyhydroxyalkanoate, 20-30 parts of polypropylene carbonate, 0.5-1 part of zinc acetate, 3-6 parts of plasticizer, 5-15 parts of antibacterial master batch, 1-4 parts of antioxidant and 0.8-3.2 parts of degradation accelerator;
the antibacterial master batch comprises: 2-6 parts of starch, 1-3 parts of polyvinyl alcohol, 0.1-0.3 part of nano titanium dioxide, 0.2-0.5 part of nano silicon dioxide, 0.25-0.5 part of soluble rare earth salt, 0.05-0.1 part of silane coupling agent and 1-3 parts of loofah sponge fiber.
By adopting the technical scheme, the polyhydroxyalkanoate is used as a main base material of a new material of the packaging bag, and the polypropylene carbonate and the zinc acetate are matched, so that the blending material with excellent comprehensive performance can be prepared, and the complete biodegradability of the material is not lost, thereby improving the mechanical effect of the polyhydroxyalkanoate and improving the tensile property of the packaging bag; the polyhydroxyalkyl acid is a degradable plastic, has good environmental effect and certain gas barrier property, so that the prepared packaging bag can prolong the fresh-keeping time of fruits and vegetables; in addition, a degradation accelerator is added, so that the degradation speed of a new packaging bag material prepared from raw materials such as polyhydroxyalkanoate, polypropylene carbonate and the like is increased; the antibacterial master batch is prepared from starch, polyvinyl alcohol, nano silicon dioxide, loofah sponge fiber and other components, the nano titanium dioxide has photocatalysis antibacterial performance, the loofah sponge fiber contains antibacterial components such as tannins and the like, the novel packaging bag material has antibacterial effect, the loofah sponge fiber has biodegradability, the degradation rate of the novel packaging bag material is not affected, the soluble rare earth salt can inhibit bacterial growth, so that the antibacterial rate of the novel packaging bag material is improved, the starch is natural high molecular polysaccharide, a certain reactivity exists for hydroxyl groups in a dehydrated glucose unit on a molecular chain, the starch can be subjected to substitution reaction with a silane coupling agent, the silane coupling agent is grafted onto the molecular chain, the hydrophobic modification of the starch is achieved, the starch and the polypropylene carbonate with hydroxyl groups at the tail end form a blending material through hydrogen bonding, the molecular chain between the starch and the polypropylene carbonate are mutually entangled and penetrated, the interfacial transmission stress of the starch and the polypropylene carbonate is improved, the dispersibility of PPC and the antibacterial master batch is improved, and the mechanical effect of the novel packaging bag material is improved.
Optionally, the preparation method of the antibacterial master batch comprises the following steps:
mixing starch, soluble rare earth salt, a silane coupling agent and distilled water, heating to 45-60 ℃, stirring for 4-5h, cooling to room temperature, filtering, washing precipitate with absolute ethyl alcohol, and vacuum drying to obtain modified starch;
adding retinervus Luffae fructus fiber into deionized water, heating to 70-80deg.C, stirring for 6-8 hr, and filtering to obtain retinervus Luffae fructus extractive solution; preparing polyvinyl alcohol into a polyvinyl alcohol aqueous solution with the mass concentration of 4-6%, adding nano titanium dioxide and nano silicon dioxide, performing ultrasonic dispersion for 20-30min, and drying to obtain pretreated polyvinyl alcohol;
mixing the loofah sponge extract with the modified starch to prepare a blending emulsion, mixing the blending emulsion with the pretreated polyvinyl alcohol, and extruding and granulating.
By adopting the technical scheme, firstly, starch and soluble rare earth salt are pretreated by a silane coupling agent, the coupling agent is grafted on starch molecules, and the soluble rare earth salt can be uniformly dispersed with the starch under the action of the silane coupling agent; the loofah extract obtained by mixing loofah fibers with deionized water and extracting with water contains substances which can be dissolved by water, such as inorganic salts, saccharides, tannins, proteins, amino acids, alkaloid salts, organic acid salts and the like, wherein the tannins and the glycosides have an antibacterial function; and mixing polyvinyl alcohol with nano titanium dioxide and nano silicon dioxide, wherein the silicon-oxygen bond of the nano silicon dioxide reacts with the hydrophilic group of the polyvinyl alcohol to change the hydrophilic property of the polyvinyl alcohol, the nano titanium dioxide is doped to improve the combination reaction effect of the silicon-oxygen bond and the hydrophilic group of the polyvinyl alcohol, fill the pores of a polyvinyl alcohol network structure, change the permeation path of water molecules, reduce the water permeability of the polyvinyl alcohol, thereby changing the water permeability of the antibacterial master batch, further reduce the water permeability of new packaging bag materials, and finally mix and extrude the pretreated polyvinyl alcohol, modified starch and luffa extract to prepare the antibacterial master batch.
Alternatively, the polyhydroxyalkanoate includes polyhydroxybutyrate and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) in a mass ratio of 0.3-0.6:1.
By adopting the technical scheme, the physical and mechanical properties of the Polyhydroxybutyrate (PHB) are similar to those of polypropylene, the PHB has biodegradability, degradation products in nature are carbon dioxide and water, the PHB also has better biocompatibility, the PHB is a degradable polymer material produced by biological fermentation, the PHB has excellent mechanical properties and biocompatibility, and the PHB are blended with polypropylene carbonate to prepare a packaging bag new material which has good flexibility and can be completely biodegraded.
Optionally, the degradation promoter is prepared by mixing and extruding the following components in parts by weight: 1 to 3 parts of polylactic acid, 0.05 to 0.1 part of organic acid, 0.5 to 1.5 parts of polyethylene glycol, 0.09 to 0.27 part of organic montmorillonite and 0.5 to 1.5 parts of EVOH.
By adopting the technical scheme, components such as polylactic acid, organic acid and the like are used for preparing the degradation accelerator, the polylactic acid has complete biodegradability and better biocompatibility, can be fully mixed with polyhydroxyalkanoate and the like, and can undergo autotrophic reaction in natural environment to generate peroxide, and the peroxide decomposes free radicals under illumination to cause the breaking degradation of a polymer chain; in addition, the polylactic acid has hydrophilicity, and the mixing of polyethylene glycol is beneficial to improving the hydrophilicity of the polylactic acid, so that the surface of the packaging bag is wetted, microorganisms are more easily attached to the surface of the packaging bag, and the degradation of the packaging bag is accelerated; in addition, the addition of EVOH and organic montmorillonite can raise the barrier property of polylactic acid to oxygen and water vapor, and can make the new material of packing bag possess hydrophilic surface and waterproof effect, and can improve the fresh-keeping capacity of packing bag for fruits and vegetables.
Optionally, the soluble rare earth salt comprises cerium humate and samarium chloride with a mass ratio of 1:0.3-0.5.
By adopting the technical scheme, the cerium humate and the samarium chloride are rare earth salts with strong antibacterial capability, can inhibit the growth of strains and improve the sterilization effect of antibacterial master batches.
Optionally, the novel packaging bag material with strong antibacterial property also comprises a preservative, and the dosage of the preservative is 4-8 parts.
By adopting the technical scheme, when the novel packaging bag material is used for packaging fruits, vegetables and other substances, the preservative is added, so that the storage time of the fruits and vegetables can be improved, and the preservation effect of the packaging bag can be prolonged.
Optionally, the preservative comprises the following components in parts by weight: 1-2 parts of aloe nano silver colloid, 5-8 parts of EVA, 1-2 parts of chitosan fiber and 0.03-0.07 part of silane coupling agent.
By adopting the technical proposal, the aloe nano silver colloid comprises aloe and nano silver particles, the nano silver particles have better antibacterial property, the aloe has barrier property after film formation, the EVA has biodegradability, good mechanical property and strong barrier property, the chitosan fiber can sterilize and antibacterial, inhibit bacterial reproduction, the silane coupling agent can improve the compatibility of the chitosan fiber, the aloe nano silver colloid and the EVA,
optionally, the chitosan fiber is prepared by pretreatment of bamboo nanocellulose whiskers, and the specific method is as follows;
mixing bamboo nanocellulose whisker with water, performing ultrasonic treatment for 20-30min to obtain bamboo nanocellulose whisker suspension, mixing and soaking the bamboo nanocellulose whisker suspension and chitosan fiber, and vacuum drying.
By adopting the technical scheme, the nanocellulose whisker is immersed on the chitosan fiber, and the special morphological structure and surface performance of the nanocellulose whisker enable the nanocellulose whisker to form a compact network structure, so that excellent oxygen barrier performance is provided, the barrier performance of the chitosan fiber to oxygen is improved, and the fresh-keeping effect of a new material of the packaging bag is improved.
Preferably, the antioxidant is selected from one or more of antioxidant 1010 and antioxidant 168; the plasticizer is one or more selected from epoxidized soybean oil, white oil, glycerin, polyethylene glycol and citric acid.
In a second aspect, the present application provides a method for preparing a packaging bag new material with strong antibacterial property, which adopts the following technical scheme:
a preparation method of a novel packaging bag material with strong antibacterial property comprises the following steps:
blending polyhydroxyalkanoate with polypropylene carbonate and zinc acetate, extruding and granulating to obtain a pretreatment master batch;
and blending the pretreatment master batch with antibacterial master batch, preservative, plasticizer, antioxidant and degradation promoter, extruding and granulating to obtain the novel packaging bag material with strong antibacterial property.
By adopting the technical scheme, the polyhydroxyalkanoate, the polypropylene carbonate and the zinc acetate are firstly blended and granulated, and the zinc acetate is used as an ester exchange catalyst, so that a blend material with excellent mechanical properties is prepared, and finally the blend material is mixed and granulated with the rest materials, the preparation method is simple, and the prepared packaging bag new material has good antibacterial property.
In summary, the present application has the following beneficial effects:
1. the novel packaging bag material is prepared from polyhydroxyalkanoate, polypropylene carbonate and the like, and the antibacterial master batch prepared from starch, polyvinyl alcohol, soluble rare earth salt and the like is doped, so that the polyhydroxyalkanoate and the polypropylene carbonate have biodegradability, the mechanical property is improved after the polyhydroxyalkanoate and the polypropylene carbonate are blended, the terminal hydroxyl groups of the polypropylene carbonate are not blocked, the polypropylene carbonate is connected with the hydroxyl groups in the starch, the compatibility of the antibacterial master batch and the polypropylene carbonate is improved, and in addition, the loofah sponge fiber, the soluble rare earth salt and the nano titanium dioxide have antibacterial property, so that the antibacterial capability of the packaging bag can be improved.
2. In the application, components such as polylactic acid, organic acid, polyethylene glycol and the like are preferably adopted to prepare the degradation accelerator, the hydrophilicity of the polylactic acid is good, the hydrophilicity of the polylactic acid can be improved by doping the polyethylene glycol, so that the surface of a new packaging bag material is hydrophilic, the adhesion of microorganisms on the surface of the new packaging bag material is facilitated, the barrier property of the polylactic acid is improved by doping the EVOH and the organic montmorillonite, the surface of the packaging bag is hydrophilic but not permeable, the degradation is facilitated, and the antibacterial and fresh-keeping effects are good.
3. The aloe nano silver colloid, the chitosan fiber, the EVA and the silane coupling agent are preferably adopted to prepare the preservative, the chitosan fiber and the aloe nano silver colloid have antibacterial property, the aloe nano silver colloid has certain barrier property, the EVA has barrier and degradable effects, and the prepared preservative can improve the moisture retention and water retention of new packaging bag materials and improve the preservation effect.
Detailed Description
Preparation examples 1-3 of antibacterial masterbatch
Preparation example 1: (1) Mixing 1kg of tapioca starch, 0.25kg of soluble rare earth salt, 0.05kg of silane coupling agent KH550 and 2kg of distilled water, heating to 45 ℃, stirring for 4 hours, cooling to room temperature, filtering, washing a precipitate with absolute ethyl alcohol, and vacuum drying at 80 ℃ for 3 hours to prepare modified starch, wherein the soluble rare earth salt comprises cerium humate and samarium chloride in a mass ratio of 1:0.3;
(2) Adding 1kg of loofah sponge fibers into 2kg of deionized water, heating to 70 ℃, stirring for 8 hours, and filtering to obtain a loofah sponge extract;
(3) 1kg of polyvinyl alcohol is prepared into a polyvinyl alcohol aqueous solution with the mass concentration of 4%, 0.1kg of nano titanium dioxide and 0.2kg of nano silicon dioxide are added, ultrasonic dispersion is carried out for 20min, and the pretreated polyvinyl alcohol is prepared by drying;
(4) Mixing the loofah sponge extract with modified starch to prepare a blending emulsion, mixing the blending emulsion with the pretreated polyvinyl alcohol, and extruding and granulating at 170 ℃.
Preparation example 2: (1) Mixing 2kg of tapioca starch, 0.5kg of soluble rare earth salt, 0.1kg of silane coupling agent KH550 and 4kg of distilled water, heating to 60 ℃, stirring for 5 hours, cooling to room temperature, filtering, washing a precipitate with absolute ethyl alcohol, and vacuum drying at 80 ℃ for 3 hours to prepare modified starch, wherein the soluble rare earth salt comprises cerium humate and samarium chloride in a mass ratio of 1:0.5; (2) Adding 3kg of loofah sponge fibers into 3kg of deionized water, heating to 80 ℃, stirring for 6 hours, and filtering to obtain a loofah sponge extract;
(3) 3kg of polyvinyl alcohol is prepared into a polyvinyl alcohol aqueous solution with the mass concentration of 6%, 0.3kg of nano titanium dioxide and 0.5kg of nano silicon dioxide are added, ultrasonic dispersion is carried out for 30min, and the pretreated polyvinyl alcohol is prepared by drying;
(4) Mixing the loofah sponge extract with modified starch to prepare a blending emulsion, mixing the blending emulsion with the pretreated polyvinyl alcohol, and extruding and granulating at 170 ℃.
Preparation example 3: uniformly mixing 2kg of tapioca starch, 1kg of polyvinyl alcohol, 0.1kg of nano titanium dioxide, 0.2kg of nano silicon dioxide, 0.25kg of soluble rare earth salt, 0.05kg of silane coupling agent KH550 and 1kg of loofah sponge fiber, extruding and granulating at 170 ℃ to prepare the antibacterial master batch, wherein the soluble rare earth salt comprises cerium humate and samarium chloride in a mass ratio of 1:0.3.
Examples
Example 1: the new packaging bag material with strong antibacterial property is shown in table 1, wherein the plasticizer is epoxidized soybean oil, the antioxidant is antioxidant 1010, the degradation promoter is prepared by mixing and extruding 1kg of polylactic acid, 0.05kg of organic acid, 0.5kg of polyethylene glycol, 0.09kg of organic montmorillonite and 0.5kg of EVOH, the polyhydroxyalkanoate comprises Polyhydroxybutyrate (PHB) and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) in a mass ratio of 0.3:1, the PHB brand is 9200, and the antibacterial masterbatch is prepared from preparation example 1.
The preparation method of the novel packaging bag material with strong antibacterial property comprises the following steps:
blending polyhydroxyalkanoate with polypropylene carbonate and zinc acetate, extruding and granulating to obtain a pretreatment master batch;
the pretreated master batch is mixed with antibacterial master batch, plasticizer, antioxidant and degradation promoter, and extruded and granulated at 170 ℃ to prepare the novel packaging bag material with strong antibacterial property.
TABLE 1 raw material usage of New packaging bag Material in examples 1-4
Example 2: a novel packaging bag material with strong antibacterial property is different from example 1 in that the raw material dosage is shown in Table 1, antibacterial master batch is prepared from preparation example 2, degradation promoter is prepared by mixing and extruding 3kg polylactic acid, 0.1kg organic acid, 1.5kg polyethylene glycol, 0.27kg organic montmorillonite and 1.5kg EVOH, and polyhydroxyalkanoate comprises Polyhydroxybutyrate (PHB) and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with the mass ratio of 0.6:1.
Examples 3-4: a new packaging bag material with strong antibacterial property is different from example 1 in that the raw material amounts are shown in Table 1.
Example 5: a novel packaging bag material with strong antibacterial property is different from example 1 in that antibacterial master batch is prepared from preparation example 3.
Example 6: a new packaging bag material with strong antibacterial property is different from example 1 in that polyethylene glycol is not added in the degradation promoter.
Example 7: a new packaging bag material with strong antibacterial property is different from example 1 in that EVOH and organic montmorillonite are not added into the degradation accelerator.
Example 8: a new packaging bag material with strong antibacterial property is different from the packaging bag material in the embodiment 1 in that the packaging bag material also contains 4kg of preservative, and the preservative is prepared by the following method: mixing 1kg of chitosan fiber, 1kg of aloe nano silver colloid, 0.03kg of silane coupling agent KH550 and 3kg of water, heating to 60 ℃, preserving heat, stirring for 2 hours, drying, mixing with 5kg of EVA, extruding and granulating; the preparation method of the aloe nano silver colloid comprises the following steps: squeezing 1kg of aloe, adding deionized water 2 times of the aloe, heating to boiling, filtering, adding silver-ammonia solution into the filtrate, and reacting at normal temperature for 2h to obtain aloe nano silver colloid with the concentration of 3.6 mg/L;
the chitosan fiber is pretreated by bamboo nanocellulose whisker, and the specific method comprises the following steps: crushing fresh bamboo into bamboo pulp, mixing the bamboo pulp with a sulfuric acid solution with the concentration of 60wt% according to the mass ratio of 1:9, stirring for 30min at 55 ℃, centrifuging, removing supernatant, washing with water to be neutral, drying to obtain bamboo nanocellulose whiskers, mixing the bamboo nanocellulose whiskers with water, carrying out ultrasonic treatment for 20min to obtain a bamboo nanocellulose whisker suspension, mixing and soaking the bamboo cellulose suspension with chitosan fibers, and carrying out vacuum drying;
the preparation method of the novel packaging bag material with strong antibacterial property comprises the following steps:
blending polyhydroxyalkanoate with polypropylene carbonate and zinc acetate, extruding and granulating to obtain a pretreatment master batch;
and blending the pretreatment master batch with antibacterial master batch, preservative, plasticizer, antioxidant and degradation promoter, extruding and granulating to obtain the novel packaging bag material with strong antibacterial property.
Example 9: a new packaging bag material with strong antibacterial property is different from the packaging bag material in the embodiment 1 in that the packaging bag material also contains 8kg of preservative, and the preservative is prepared by the following method: mixing 2kg of chitosan fiber, 2kg of aloe nano silver colloid, 0.07kg of silane coupling agent KH550 and 3kg of water, heating to 60 ℃, preserving heat, stirring for 2 hours, drying, mixing with 8kg of EVA, extruding and granulating; the preparation method of the aloe nano silver colloid comprises the following steps: squeezing 1kg of aloe, adding deionized water 2 times of the aloe, heating to boiling, filtering, adding silver-ammonia solution into the filtrate, and reacting at normal temperature for 2h to obtain aloe nano silver colloid with the concentration of 3.6 mg/L;
the chitosan fiber is pretreated by bamboo nanocellulose whisker, and the specific method comprises the following steps: crushing fresh bamboo into bamboo pulp, mixing the bamboo pulp with a sulfuric acid solution with the concentration of 60wt% according to the mass ratio of 1:9-, stirring for 30min at 55 ℃, centrifuging, removing supernatant, washing with water to be neutral, drying to obtain bamboo nanocellulose whiskers, mixing the bamboo nanocellulose whiskers with water, carrying out ultrasonic treatment for 20min to obtain a bamboo nanocellulose whisker suspension, mixing and soaking the bamboo cellulose suspension with chitosan fibers, and carrying out vacuum drying.
Example 10: a new packaging bag material with strong antibacterial property is different from example 9 in that chitosan fibers are not pretreated by bamboo nanocellulose whiskers.
Example 11: a new packaging bag material with strong antibacterial property is different from example 9 in that aloe nano silver colloid is not added in the preservative.
Example 12: a new packaging bag material with strong antibacterial property is different from example 9 in that chitosan fiber is not added.
Example 13: a new packaging bag material having a high antibacterial property is different from example 9 in that EVA is not added.
Example 14: a new packaging bag material with strong antibacterial property is different from example 9 in that the preservative is sodium alginate.
Comparative example
Comparative example 1: a new packaging bag material with strong antibacterial property is different from the packaging bag material in the embodiment 1 in that nano titanium dioxide and nano silicon dioxide are not added into antibacterial master batches.
Comparative example 2: a new packaging bag material with strong antibacterial property is different from the packaging bag material in the embodiment 1 in that no loofah sponge fiber is added in antibacterial master batches.
Comparative example 3: a new packaging bag material with strong antibacterial property is different from example 1 in that no soluble rare earth salt is added in antibacterial master batch.
Comparative example 4: a new packaging bag material having a high antibacterial property is different from example 1 in that no degradation promoter is added.
Comparative example 5: the polyethylene material for the food packaging bag comprises the following raw materials in parts by weight: 80g of polyethylene, 20g of methyl methacrylate-butadiene-styrene copolymer, 4g of talcum powder, 2g of organic nano montmorillonite, 2g of modified graphene, 0.3g of stearic acid, 1g of polyethylene grafted maleic anhydride copolymer and 1g of silane coupling agent;
in the preparation process of the modified graphene, 0.4268g (0.002 mol) of dodecyl dimethyl tertiary amine is dissolved in 100ml of ethanol, 0.4769g (0.0024 mol) of 3-chloropropyl trimethoxysilane is added and uniformly mixed, the temperature is raised to 60 ℃ in a water bath, the temperature is kept for 48 hours, and the ethanol is removed by reduced pressure evaporation to obtain an intermediate material; uniformly dispersing 5g of graphene oxide in 300ml of ethanol by ultrasonic, adding 20ml of ethanol water solution containing 0.25g of intermediate material, uniformly mixing, carrying out grafting reaction for 4 hours at 85 ℃ under heat preservation and stirring, filtering, washing a filter cake, and drying to obtain the modified graphene.
Performance test
New materials for packaging bags were prepared according to the methods of examples and comparative examples, and various properties were measured according to the following methods, and the measurement results are recorded in table 2.
1. Antibacterial properties: the detection is carried out according to GB/T31402-2015 test method for antibacterial property of plastic surface, and the detection is carried out uniformly on escherichia coli (ATCC 25922) and staphylococcus aureus (ACTT 6538);
2. weight loss degradation rate: burying the new material prepared in the examples or the comparative examples in a constant-humidity closed container containing soil with pH value of 6-7, taking out on 83 th day, washing with deionized water, drying, balancing at room temperature for 24 hours, weighing, and calculating degradation rate, wherein the degradation rate (%) = (mass before degradation-mass after degradation)/mass before degradation is multiplied by 100%;
3. tensile strength: adding the new material prepared in the example or the comparative example into a film blowing machine for film blowing treatment, blowing out a film at 120 ℃, cooling the film to normal temperature, preparing a packaging bag with the thickness of 1.1mm, and detecting according to GB/T1040-2006 determination of plastic stretching property;
4. the fresh-keeping effect is as follows: the new material prepared in the example or the comparative example is added into a film blowing machine to carry out film blowing treatment, the film is blown out at 120 ℃, then the film is cooled to normal temperature, a packaging bag with the thickness of 1.1mm is prepared, the water vapor transmission rate is detected according to GB/T1037-1988 "method for testing plastic film and sheet Water vapor permeation test", and the oxygen transmission rate is detected according to GB/T31354-2014 "method for testing package and container oxygen transmission.
TABLE 2 Performance test of packaging bag New Material with high antibacterial Property
By combining the data in examples 1-4 and Table 2, it can be seen that the novel packaging bag material prepared in examples 1-4 has high antibacterial effect on Escherichia coli and Staphylococcus aureus, and has a degradation rate of more than 80% at 83 days, high tensile strength and good mechanical properties.
In example 5, the antibacterial master batch prepared in preparation example 3 was used, and the antibacterial master batch was prepared by simply mixing the respective raw materials, and the antibacterial property of the novel packaging bag material prepared in example 5 was lowered as compared with example 1.
In example 6, polyethylene glycol was not added to the degradation accelerator compared with example 1, and the degradation rate was reduced after the new packaging bag material prepared in example 6 was left in the soil for 83 days, indicating that polyethylene glycol can improve the biodegradation rate of the new packaging bag material.
Compared with example 1, example 7 has no organic montmorillonite added in the degradation accelerator, and as can be seen from the data in table 2, the new packaging bag material prepared in example 7 has reduced barrier effect on oxygen and water vapor, increased permeability of oxygen and water vapor and reduced tensile strength, which indicates that the addition of EVOH and organic montmorillonite can effectively improve the barrier property of the new packaging bag material, improve the fresh-keeping effect and improve the mechanical strength.
Compared with the example 1, the example 8 and the example 9 are also added with the antistaling agent, and the data in the table 2 show that the antibacterial effect of the novel packaging bag materials prepared in the example 8 and the example 9 is improved, and the novel packaging bag materials still have higher degradation rate, obviously lower water vapor and oxygen transmission rate, improved barrier property and improved fresh-keeping effect.
Compared with example 9, the chitosan fiber is not pretreated by the bamboo nanocellulose whisker, the novel packaging bag material prepared in example 10 has reduced blocking effect on oxygen and water vapor, and the fresh-keeping effect is reduced.
Compared with example 9, in example 11 and example 12, aloe nano silver colloid is not added in example 11, chitosan fiber is not added in example 12, the antibacterial rate of the novel packaging bag materials prepared in example 11 and example 12 is reduced, the antibacterial effect is weakened, the transmittance of oxygen and water vapor is increased, and the fresh-keeping effect is reduced.
In example 13, the fresh-keeping agent was not added with EVA, and the remaining properties of the new material for the packaging bag prepared in example 13 were not changed much, but the barrier properties to water vapor and oxygen were reduced, as compared with example 9.
In the embodiment 14, sodium alginate is used as a preservative, the barrier property of a new material of the packaging bag is obviously reduced, and the preservation effect is weakened.
Comparative example 1 compared with example 1, no nano titanium dioxide and nano silicon dioxide are added, and the antibacterial and fresh-keeping properties of the material prepared in comparative example 1 are reduced as shown in table 2.
Compared with the example 1, the novel packaging bag material prepared in the comparative example 2 has the advantages that the antibacterial property is reduced, the degradation rate is not changed greatly, the blocking effect is not obviously improved, and the novel packaging bag material has no influence on the degradation rate.
Comparative example 3 compared with example 1, no soluble rare earth salt was added, and as can be seen from the data in table 2, the addition of the soluble rare earth salt improved the antibacterial property of the new packaging bag material.
Comparative example 4 the degradation rate of the new material for the packaging bag manufactured in comparative example 4 was significantly reduced and the barrier properties to water vapor and oxygen were reduced, compared with example 1, without the addition of the degradation promoter.
Comparative example 5 is a packaging material prepared in the prior art, and has small antibacterial rate, poor antibacterial effect and difficult degradation.
The new materials prepared in the examples 1 and 8-14 are used for preparing packaging bags, the fresh-keeping effect is tested at 35 ℃ under the environment of 65%, the tested object is cherries, the cherries packaged in the example 1 are rotted on the 3 rd day, the cherries packaged in the examples 8 and 9 are rotted on the 8 th day, the cherries packaged in the examples 12 and 13 are rotted on the 5 th day, and the cherries packaged in the examples 11 and 10 are rotted on the 7 th day, so that the new materials prepared by doping the preservative in the examples 8 and 9 can ensure that the packaging bags have better compactness and better fresh-keeping effect, and are beneficial to realizing the prolongation of the fresh-keeping period of fruits and vegetables and realizing the long-term fresh keeping of fruits and vegetables.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The novel packaging bag material with strong antibacterial property is characterized by comprising the following components in parts by weight: 60-90 parts of polyhydroxyalkanoate, 20-30 parts of polypropylene carbonate, 0.5-1 part of zinc acetate, 3-6 parts of plasticizer, 5-15 parts of antibacterial master batch, 1-4 parts of antioxidant and 0.8-3.2 parts of degradation accelerator;
the antibacterial master batch comprises: 2-6 parts of starch, 1-3 parts of polyvinyl alcohol, 0.1-0.3 part of nano titanium dioxide, 0.2-0.5 part of nano silicon dioxide, 0.25-0.5 part of soluble rare earth salt, 0.05-0.1 part of silane coupling agent and 1-3 parts of loofah sponge fiber.
2. The strong antibacterial packaging bag new material according to claim 1, characterized in that: the preparation method of the antibacterial master batch comprises the following steps:
mixing starch, soluble rare earth salt, a silane coupling agent and distilled water, heating to 45-60 ℃, stirring for 4-5h, cooling to room temperature, filtering, washing precipitate with absolute ethyl alcohol, and vacuum drying to obtain modified starch;
adding retinervus Luffae fructus fiber into deionized water, heating to 70-80deg.C, stirring for 6-8 hr, and filtering to obtain retinervus Luffae fructus extractive solution;
preparing polyvinyl alcohol into a polyvinyl alcohol aqueous solution with the mass concentration of 4-6%, adding nano titanium dioxide and nano silicon dioxide, performing ultrasonic dispersion for 20-30min, and drying to obtain pretreated polyvinyl alcohol;
mixing the loofah sponge extract with the modified starch to prepare a blending emulsion, mixing the blending emulsion with the pretreated polyvinyl alcohol, and extruding and granulating.
3. The novel antibacterial packaging bag material according to claim 1, wherein the polyhydroxyalkanoate comprises polyhydroxybutyrate and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) in a mass ratio of 0.3-0.6:1.
4. The novel packaging bag material with strong antibacterial property according to claim 1, wherein the degradation promoter is prepared by mixing and extruding the following components in parts by weight: 1 to 3 parts of polylactic acid, 0.05 to 0.1 part of organic acid, 0.5 to 1.5 parts of polyethylene glycol, 0.09 to 0.27 part of organic montmorillonite and 0.5 to 1.5 parts of EVOH.
5. The strong antibacterial packaging bag new material according to claim 1, wherein the soluble rare earth salt comprises cerium humate and samarium chloride in a mass ratio of 1:0.3-0.5.
6. The new packaging bag material with strong antibacterial property according to claim 1, wherein the new packaging bag material with strong antibacterial property further comprises a preservative in an amount of 4-8 parts.
7. The novel packaging bag material with strong antibacterial property according to claim 6, wherein the preservative comprises the following components in parts by weight: 1-2 parts of aloe nano silver colloid, 5-8 parts of EVA, 1-2 parts of chitosan fiber and 0.03-0.07 part of silane coupling agent.
8. The novel packaging bag material with strong antibacterial property according to claim 7, wherein the chitosan fiber is prepared by pretreatment of bamboo nanocellulose whisker, and the specific method is as follows;
mixing bamboo nanocellulose whisker with water, performing ultrasonic treatment for 20-30min to obtain bamboo nanocellulose whisker suspension, mixing and soaking the bamboo nanocellulose whisker suspension and chitosan fiber, and vacuum drying.
9. The novel packaging bag material with strong antibacterial property according to claim 1, wherein the antioxidant is one or more selected from the group consisting of antioxidant 1010 and antioxidant 168; the plasticizer is one or more selected from epoxidized soybean oil, white oil, glycerin, polyethylene glycol and citric acid.
10. The method for preparing a new packaging bag material with strong antibacterial property as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
blending polyhydroxyalkanoate with polypropylene carbonate and zinc acetate, extruding and granulating to obtain a pretreatment master batch;
and blending the pretreatment master batch with antibacterial master batch, preservative, plasticizer, antioxidant and degradation promoter, extruding and granulating to obtain the novel packaging bag material with strong antibacterial property.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116875004A (en) * | 2023-08-23 | 2023-10-13 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
| CN117511159A (en) * | 2024-01-05 | 2024-02-06 | 湖南大道新材料有限公司 | Cosmetic dry-wet separation packaging bag |
-
2023
- 2023-03-01 CN CN202310182449.3A patent/CN116218173A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116875004A (en) * | 2023-08-23 | 2023-10-13 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
| CN116875004B (en) * | 2023-08-23 | 2024-03-26 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
| CN117511159A (en) * | 2024-01-05 | 2024-02-06 | 湖南大道新材料有限公司 | Cosmetic dry-wet separation packaging bag |
| CN117511159B (en) * | 2024-01-05 | 2024-03-22 | 湖南大道新材料有限公司 | Cosmetic dry-wet separation packaging bag |
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