CN116875004B - PBAT master batch, preparation method thereof and PBAT preservative film - Google Patents
PBAT master batch, preparation method thereof and PBAT preservative film Download PDFInfo
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- CN116875004B CN116875004B CN202311063862.4A CN202311063862A CN116875004B CN 116875004 B CN116875004 B CN 116875004B CN 202311063862 A CN202311063862 A CN 202311063862A CN 116875004 B CN116875004 B CN 116875004B
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- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 92
- 230000002335 preservative effect Effects 0.000 title claims abstract description 87
- 239000003755 preservative agent Substances 0.000 title claims abstract description 86
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
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- 230000003449 preventive effect Effects 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 239000000377 silicon dioxide Substances 0.000 claims description 39
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 13
- 229910021426 porous silicon Inorganic materials 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
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Abstract
The application relates to the field of high polymer materials, and particularly discloses a PBAT master batch, a preparation method thereof and a PBAT preservative film. The PBAT master batch comprises the following raw materials in parts by weight: 20-50 parts of PBAT, 0.5-2 parts of lubricant, 0.5-2 parts of antioxidant, 2-3 parts of compatilizer, 5-15 parts of inorganic micro powder, 5-10 parts of hygroscopic material, 5-10 parts of organic porous material and 0.6-2.2 parts of mildew preventive. The PBAT master batch can be used for preparing PBAT preservative films, and has the advantages of difficult condensation water drop on the inner surface of the preservative films, good moisture permeability effect and strong preservation capability.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a PBAT master batch, a preparation method thereof and a PBAT preservative film.
Background
At present, in daily production and life, the preservative film is widely applied to household life and part of packaging industry, and the plastic preservative film widely applied is basically a traditional petroleum-based PE preservative film. The preservative film is very thin, so that the preservative film is difficult to recycle, and the preservative film is not degraded in nature after being abandoned, so that white pollution is caused.
The PBAT is a copolymer of poly (adipic acid) and poly (butylene terephthalate), has excellent biodegradability, has the characteristics of PBT and PBAT, has good ductility and elongation at break, and has good heat resistance and impact property, so that the PBAT is currently concerned by experts and scholars in all countries, and becomes one of the hot spots of the current biodegradable plastic research.
In the prior art, the Chinese patent document with the application number of CN201811189636.X discloses a biodegradable preservative film which is mainly prepared from the following raw materials in parts by weight: 50-65 parts of PBAT, 20-40 parts of polylactic acid, 15-30 parts of modified starch, 3-10 parts of biodegradable aliphatic-aromatic copolyester, 3-10 parts of methyl hydroxypropyl cellulose ether, 2-8 parts of nano talcum powder, 0.1-0.5 part of chain extender, 0.2-0.8 part of antioxidant and 0.2-0.6 part of lubricant.
Aiming at the related technology, the inventor finds that the existing biodegradable preservative film has better biodegradability, toughness, plasticity and strength, but when the biodegradable preservative film is used for preserving fruits and vegetables, the respiration of the fruits and vegetables is generated on the inner wall of the preservative film, so that bacteria are easy to breed and mildew, and further the decay of the fruits and vegetables is accelerated.
Disclosure of Invention
In order to improve the anti-condensation effect of the PBAT preservative film and prolong the preservation capacity, the application provides a PBAT master batch, a preparation method thereof and the PBAT preservative film.
In a first aspect, the present application provides a PBAT master batch, which adopts the following technical scheme:
the PBAT master batch comprises the following raw materials in parts by weight: 20-50 parts of PBAT, 0.5-2 parts of lubricant, 0.5-2 parts of antioxidant, 2-3 parts of compatilizer, 5-15 parts of inorganic micro powder, 5-10 parts of hygroscopic material, 5-10 parts of organic porous material and 0.6-2.2 parts of mildew preventive.
By adopting the technical scheme, the moisture absorption material and the organic porous material are added in the PBAT master batch, when the PBAT master batch is made into the preservative film, the fruit and vegetable is packaged, the fruit and vegetable generates water mist due to the respiration effect in the preservative film, the moisture absorption material has strong water absorption, when the water vapor reaches the preservative film, the preservative film absorbs the water vapor, and after the water vapor reaches a certain concentration, the water vapor is slowly released into the preservative film, so that the water loss of the fruit and vegetable is effectively inhibited, and meanwhile, the mildew inhibitor can prevent the fruit and vegetable and the like from mildew; the porous structure of the organic porous material can enable ethylene released by fruits and vegetables to be discharged from the preservative film, and when water vapor generated in the preservative film cannot be completely absorbed by the moisturizing material, the water vapor is convenient to release from the preservative film, so that the water vapor is difficult to be absorbed by the moisturizing material and is condensed on the inner surface of the preservative film to form fog drops; when the PBAT master batch is formed into a film by melt blow molding, the inorganic micro powder is separated from the PBAT by stretching to form micropores, so that the permeation of water vapor is facilitated.
Optionally, the moisture absorption material comprises super absorbent resin and porous silica, and the mass ratio of the super absorbent resin to the porous silica is 0.3-0.5:1.
Through adopting above-mentioned technical scheme, super absorbent resin can absorb the vapor that fruit vegetables produced, porous silica has abundant pore structure, there is a large amount of mesopores and macroporous structure, can be as the storage space of adsorbed water molecule, when vapor partial pressure is higher than the saturated vapor pressure of water on the concave liquid level in the pore in the air, vapor is adsorbed, if reverse, then take place the desorption, super absorbent resin and porous silica cooperation, can absorb the vapor that fruit vegetables produced because of the respiratory effect, and silica can also release vapor when absorbing saturation, make fruit vegetables keep fresh.
Optionally, the porous silica is pretreated by:
mixing magnesium oxide and porous silicon dioxide, adding sodium hydroxide, crystalline aluminum chloride and distilled water, heating to 110-120deg.C, stirring for 8-10 hr, filtering, and oven drying.
Through adopting above-mentioned technical scheme, the porous silica surface cladding after the hydrothermal treatment has a large amount of slice aluminium hydroxide, the porous silica surface is through depositing the cladding back, slice aluminium hydroxide has increased porous silica's specific surface area, has increased the collision probability of hydrone and porous silica, help the vapor molecule to adsorb on the porous silica, porous silica's pore structure and slice aluminium hydroxide can produce great physical adsorption to the hydrone through van der Waals ' force, porous silica natural pore structure provides place and passageway for the storage and the transportation of hydrone, be favorable to the moisture absorption and the moisture release of plastic wrap, the magnesium oxide adds then can make porous silica have antibacterial, mould proof effect, thereby improve the anticorrosive of plastic wrap, the ability of extension shelf life.
Optionally, the mesoporous silica is pretreated by the following raw materials in parts by weight: 1.5 to 3.5 parts of magnesium oxide, 5 to 10 parts of porous silicon dioxide, 1 to 2 parts of sodium hydroxide, 2 to 4 parts of crystalline aluminum chloride and 25 to 50 parts of distilled water.
By adopting the technical scheme, the porous silica is pretreated by the components with the above dosage, so that the porous silica with good hygroscopicity and strong antibacterial effect can be obtained.
Alternatively, the organic porous material comprises trimellitic aldehyde and octanediamine in a molar ratio of 1.8-2:3.
By adopting the technical scheme, the amino in the octanediamine and the carbonyl in the trimellitic aldehyde can be subjected to the condensation Schiff base reaction to form imine bonds, so that the superhydrophobic covalent organic porous material is prepared, the superhydrophobic organic porous material has a micropore and mesoporous pore structure, when the water vapor contacts the inner surface, the superhydrophobic surface can reduce the adhesion of the water vapor on the inner surface of the preservative film to a certain extent, the porous structure can facilitate the permeation of the water vapor, and the surface of the organic porous material is superhydrophobic, so that the organic porous material can be well dispersed in the PBAT master batch, a certain gap is formed between the organic porous material and the PBAT matrix, the free volume of water vapor permeation is increased, and on the other hand, the pores provide channels for the water vapor permeation and improve the moisture permeability.
Optionally, the organic porous material is pretreated by:
placing the organic porous material into a lithium chloride solution with the mass fraction of 25-30%, heating to 60-80 ℃, stirring for 80-90min, vacuum filtering, drying, and grinding, wherein the mass ratio of the organic porous material to the lithium chloride solution is 1:13-15.
By adopting the technical scheme, the lithium chloride is adopted to pretreat the organic porous material, the specific surface area and specific solvent of the organic porous material are reduced, the average pore diameter is increased, the physical adsorption of the organic porous material is promoted, the moisture absorption capacity of the organic porous material is greatly improved, but the lithium chloride with too high solubility can be excessively deposited on the surface of the organic porous material to block partial pits of the organic porous material, and the moisture absorption capacity is reduced; the organic porous material is fully distributed with a plurality of pore channels and is arranged with dense micropore structures, after the organic porous material is deposited by lithium chloride, the surface is adsorbed with lithium chloride, the pore diameter is increased, the surface becomes rough and irregular, but the original porous shape is not destroyed and changed, thereby improving the humidity adjusting performance.
Optionally, 3-7 parts of demister is further contained in the PBAT master batch, and the demister is prepared by circularly dipping the loofah sponge fiber into graphene oxide dispersion liquid after pickling, and then drying, reducing and washing.
By adopting the technical scheme, when fruits and vegetables breathe, a part of released energy is dissipated in a heat form, so that water mist can be condensed on the inner surface of the preservative film, the graphene oxide is circularly immersed on the loofah sponge fibers, reduced graphene oxide is formed after reduction, the main components of the loofah sponge fibers are cellulose, and the modified graphene oxide also contain a certain amount of vitamin C, organic acid and other components, has an antibacterial and bacteriostatic effect, and the natural network structure of the modified graphene oxide is wrapped on the surfaces of the loofah sponge fibers, the reduced graphene oxide is a super-hydrophobic material, when the modified graphene oxide is continuously distributed on the loofah sponge fibers, the loofah sponge fiber liquid is endowed with super-hydrophobic property, so that the dispersion of the modified graphene oxide and the PBAT is good, the modified graphene oxide can be uniformly dispersed in PBAT master batches, and the heat transfer performance of the loofah sponge fibers is improved, the three-dimensional structure of the loofah sponge fibers provides an effective channel for phonon transmission, the scattering of phonons in the transmission process is reduced, the heat transmission between networks is promoted, the pbAT heat dissipation effect of the loofah sponge fibers is improved, the heat dissipation effect of the PBAT is improved, and the heat dissipation effect of the PBAT is reduced, and the vapor accumulated on the preservative film is reduced, and the vapor accumulated on the surface of the preservative film is reduced, and the vapor is accumulated on the surface of the preservative film is reduced; in addition, the addition of the loofah network fiber can also increase the bacteriostasis of the PBAT master batch, improve the tensile strength of the PBAT master batch and improve the stretch resistance of the PBAT master batch.
Optionally, the inorganic micro powder is at least one selected from calcium carbonate powder, talcum powder, quartz powder, montmorillonite powder and gypsum powder.
By adopting the technical scheme, after the inorganic micro powder is mixed with the PBAT, the inorganic micro powder is separated from the PBAT to generate micropores when the mixture is blown into a film, so that the air permeability and the moisture permeability are improved.
Preferably, the mildew inhibitor is at least one selected from sorbate, citrate, dehydroacetate, xanthoxylin and catechin;
the lubricant is one or more of EBS, erucamide, oleamide and zinc stearate;
the antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri (2, 4-di-tert-butylphenyl) phosphite.
By adopting the technical scheme, the mildew preventive can improve the fresh-keeping capability of the fresh-keeping film and prevent fruits and vegetables from rotting; the antioxidant can improve the oxidation resistance of PBAT, and the service life of the preservative film is prolonged better; the lubricant can enable the PBAT master batch to have better opening property and better service performance after being subjected to blow molding film formation.
In a second aspect, the present application provides a method for preparing a PBAT master batch, which adopts the following technical scheme:
the preparation method of the PBAT master batch comprises the following steps:
weighing the raw materials according to the raw material dosage of the PBAT master batch, uniformly mixing, melting, extruding and granulating.
In a third aspect, the present application provides a PBAT preservative film, which adopts the following technical scheme:
the PBAT preservative film comprises the following raw materials in parts by weight: 40-60 parts of PBAT master batch, 10-20 parts of PLA, 0.1-0.5 part of antioxidant, 0.2-1 part of plasticizer, 0.2-1 part of chain extender and 10-20 parts of coupling modified nano calcium carbonate.
By adopting the technical scheme, when the preservative film made of the PBAT master batch is used for preserving and packaging fruits and vegetables, water mist is not easy to condense on the inner surface, and the quality guarantee period of the fruits and vegetables is prolonged.
In summary, the present application has the following beneficial effects:
1. because the hygroscopic material and the organic porous material are added in the PBAT master batch, the hygroscopic material and the organic porous material can absorb the water vapor generated by fruits and vegetables, reduce the condensation of the water vapor on the inner surface of the preservative film, prevent the condensed water mist from dripping on the packaged fruits and vegetables to cause the decay of the fruits and vegetables, and further improve the anti-corrosion capability of the preservative film due to the added mildew preventive; and the moisture absorption material can release the water vapor into the preservative film after the water vapor is absorbed and saturated so as to increase the moisture content of fruits and vegetables, reduce the weight loss rate of the fruits and vegetables and keep the freshness of the fruits and vegetables.
2. In the application, magnesium oxide, magnesium hydroxide, crystalline aluminum chloride and the like are preferably adopted to pretreat the porous silicon dioxide, the surfaces of the porous silicon dioxide and the magnesium oxide are wrapped with flaky aluminum hydroxide, the specific surface area of the porous silicon dioxide is increased, the water adsorption capacity of the porous silicon dioxide is improved, the moisture absorption and release effects of the porous silicon dioxide are improved, the absorption capacity of the preservative film on water vapor is further improved, and the inner surface is prevented from condensing into water drops; and the addition of the magnesium oxide enables the porous silicon dioxide to have mildew-proof and antibacterial effects, thereby enhancing the antibacterial effects of the PBAT master batch and prolonging the shelf life of fruits and vegetables.
3. The application preferably adopts lithium chloride solution to treat the organic porous material, the organic porous material is prepared by reacting octanediamine and trimesic aldehyde through Schiff base, lithium chloride is deposited on the surface of the organic porous material, the porosity of the organic porous material is improved, the organic porous material is hydrophobic, the permeation of water vapor is facilitated, and the moisture permeability of the preservative film is improved.
4. The application preferably adopts the loofah sponge fiber to circularly impregnate the graphene oxide and reduce and prepare the demisting agent, the reduced graphene oxide has hydrophobicity, after the surface of the loofah sponge fiber is coated by deposition, the hydrophobicity of the loofah sponge fiber can be increased, the water penetration effect is improved, the heat dissipation effect of the loofah sponge fiber can be increased, more steam evaporation of fruits and vegetables caused by larger heat in the preservative film can be prevented, the fruits and vegetables are dehydrated more and the freshness is reduced, in addition, the loofah sponge fiber also has an antibacterial effect, and the mechanical strength of the preservative film can be enhanced.
Detailed Description
Preparation example 1 of organic porous Material
Preparation example 1: dimethyl sulfoxide is used as a solvent, a solution of octanediamine and trimesic aldehyde with the concentration of 0.15mol/L is prepared, wherein the molar ratio of the octanediamine to the trimesic aldehyde is 3:2, 2.5 mu L of octanoic acid is added as a catalyst, the mixture is stood still to obtain milky gel, and ethanol solutions with the mass fractions of 20%, 40%, 60%, 80% and 99.7% are respectively used for carrying out gradient solvent replacement, the total solvent replacement is carried out for 2d, the mixture is subjected to vacuum freeze drying for 24h, and the mixture is crushed to obtain the organic porous material with the particle size of 0.02 mm.
Examples
Example 1: the PBAT master batch comprises the raw materials with the dosage shown in a table 1, wherein the brand of PBAT is C1200, the lubricant is erucamide, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), the compatilizer is ethylene-acrylic ester-maleic anhydride copolymer, the mildew inhibitor is citrate, the inorganic micro powder is calcium carbonate micro powder with the particle size of 500 meshes, the moisture absorption material comprises super absorbent resin and porous silicon dioxide with the mass ratio of 0.5:1, and the organic porous material is prepared from preparation example 1, wherein the super absorbent resin is polyvinyl alcohol.
The preparation method of the PBAT master batch comprises the following steps: according to the raw material dosage of the PBAT master batch in Table 1, the raw materials are weighed, uniformly mixed, melted, extruded and granulated, the temperature of an extrusion die head is 125 ℃, and the length-diameter ratio of an extruder is 45:1.
TABLE 1 raw materials and amounts of PBAT masterbatch in examples 1-3
| Raw materials/kg | Example 1 | Example 2 | Example 3 |
| PBAT | 35 | 50 | 20 |
| Lubricant | 1.5 | 3 | 0.5 |
| Antioxidant | 1.5 | 2 | 0.5 |
| Compatibilizing agent | 2.5 | 3 | 2 |
| Inorganic micropowder | 12 | 15 | 5 |
| Moisture-absorbing material | 8 | 10 | 5 |
| Organic porous material | 8 | 10 | 5 |
| Mildew preventive | 1.2 | 2.2 | 0.6 |
Examples 2-3: the PBAT master batch differs from example 1 in that the amounts of raw materials are shown in table 1.
Example 4: the PBAT master batch is different from example 1 in that the hygroscopic material is all of a super absorbent resin.
Example 5: the PBAT master batch differs from example 1 in that the hygroscopic material is entirely porous silica.
Example 6: the PBAT master batch differs from example 1 in that the porous silica has been pretreated as follows: 2.5kg of magnesium oxide and 8kg of porous silica were mixed, 1.5kg of sodium hydroxide, 3kg of crystalline aluminum chloride and 40kg of distilled water were added, and stirred for 10 hours at 110℃and filtered and dried.
Example 7: the PBAT master batch differs from example 6 in that no magnesium oxide was added.
Example 8: the PBAT master batch differs from example 6 in that the organic porous material is pretreated by: and placing 8kg of organic porous material into a lithium chloride solution with the mass fraction of 30%, heating to 80 ℃, stirring for 80min, vacuum filtering, drying, and grinding, wherein the mass ratio of the organic porous material to the lithium chloride solution is 1:15.
Example 9: the PBAT master batch differs from example 8 in that it further comprises 7kg of a defogging agent, and the defogging agent is a perfluoroalkanolamide.
Example 10: the PBAT master batch differs from example 8 in that it further contains 7kg of a defogging agent, which is prepared by the following method: washing retinervus Luffae fructus fiber with sulfuric acid solution of concentration 1g/L for 10min, washing with distilled water, adding into graphene oxide dispersion of concentration 2mg/ml, suction filtering, circularly soaking and suction filtering for 6 times, vacuum drying at 80deg.C for 8 hr, then reducing soaking in hydroiodic acid solution of 90deg.C for 30s, washing with deionized water and ethanol, and drying at 80deg.C.
Comparative example
Comparative example 1: the PBAT master batch is different from example 1 in that no hygroscopic material is added.
Comparative example 2: the PBAT master batch is different from example 1 in that no organic porous material is added.
Application example
Application example 1: the PBAT preservative film comprises the following raw materials in parts by weight: 60kg of PBAT master batch prepared in example 1, 10kg of PLA with model FY804, 0.3kg of antioxidant 1010, 0.2kg of plasticizer (tributyl citrate), 0.2kg of chain extender (ADR-4370S) and 10kg of coupling modified nano calcium carbonate, wherein the coupling modified nano calcium carbonate is prepared by kneading nano calcium carbonate and a coupling agent KH550 according to the mass ratio of 99.5:0.5 at 80 ℃ for 30 min.
The preparation method of the PBAT preservative film comprises the following steps: the PBAT master batch, PLA, antioxidant 1010, plasticizer, chain extender and coupling modified nano calcium carbonate are uniformly mixed, melted by a screw extruder with the length-diameter ratio of 30:1, extruded and blown into a film, and the PBAT preservative film with the thickness of 10 mu m is prepared, wherein the extrusion temperature is 170 ℃.
Application example 2: the PBAT preservative film is different from the application example 1 in that PBAT master batch is prepared from the preparation example 2.
Application examples 3-10: the PBAT preservative film is different from the application example 1 in that PBAT master batches are respectively prepared from examples 3-10.
Application examples 11-12: the PBAT preservative film is different from the application example 1 in that the PBAT master batch is prepared from comparative example 1 and comparative example 2, respectively.
Application example 13: a biodegradable preservative film is prepared by the following components in parts by weight: step a, mixing 50 parts of tapioca starch and 50 parts of distilled water at 20 ℃ and uniformly stirring, adding 4 parts of glycerol and 0.6 part of maleic anhydride, and continuously stirring to form a colloidal mixture; then placing the mixture into a water bath or an oil bath for heating and gelatinizing at 95 ℃ for 25min to obtain a viscous colloid; placing the viscous colloid into an oven, baking at 100 ℃ for 15min, and crushing the dried solid to 200 meshes to obtain the modified starch.
Step b, respectively weighing 20 parts of modified starch, 50 parts of PBAT, 25 parts of polylactic acid, 3 parts of biodegradable aliphatic-aromatic copolyester, 5 parts of methyl hydroxypropyl cellulose ether and 5 parts of nano talcum powder (the average particle size is 50 nm), and drying at 75 ℃ for 4 hours to ensure that the water content of each component is less than or equal to 0.08%; stirring and dry-mixing the dried components except the nano talcum powder until the components are uniform to obtain a premix; then adding 0.2 part of chain extender ADR-4368C, 0.4 part of tert-butyl hydroquinone, 0.2 part of zinc stearate and 1 part of antibacterial agent, and continuously and uniformly stirring to obtain a blend;
in the step, the biodegradable aliphatic-aromatic copolyester is a mixture of polybutylene terephthalate-co-adipate, polyethylene terephthalate-co-adipate and polyethylene terephthalate-co-succinate according to a weight ratio of 2:2:1; the antibacterial agent is prepared by compounding nisin and tea polyphenol according to a weight ratio of 3:1.
And c, adding the blend into a screw extruder from a feeding port, adding the dried nano talcum powder into the screw extruder at the downstream of the screw, performing high-temperature melt extrusion, and cooling after film formation by blow molding to obtain the preservative film. In the step, the feeding speed of the screw extruder is 1.4rpm, the temperature of the feeding section is controlled at 60 ℃, and the temperature of each heating area of the screw extruder is controlled by the following steps: first 175 ℃, second 172 ℃, third 172 ℃, fourth 170 ℃, fifth 158 ℃, sixth 155 ℃ and nozzle 180 ℃.
Application example 14: an antifogging preservative film comprises the following components in percentage by weight: 2 parts of polyvinyl alcohol, 12 parts of soy protein isolate, 0.3 part of polyethylene glycol, 1.8 parts of glutaraldehyde, 0.3 part of acetic acid and 90 parts of water. The preparation method of the anti-fog preservative film comprises the following steps: dissolving acetic acid in water, adding soybean protein isolate, heating to 70deg.C, stirring to dissolve completely, adding polyvinyl alcohol, polyethylene glycol and glutaraldehyde, stirring to obtain viscous sol, pouring into a twin-screw extruder, extruding, plasticating, and blowing film. The temperature of the extrusion zones 1 to 5 is 115 ℃, 135 ℃, 155 ℃, 175 ℃, the temperature of the machine head is 155 ℃ and the rotating speed is 20r/min. The extrusion granulating temperature of the raw materials in the film blowing process is 135 ℃, 155 ℃, 165 ℃, 160 ℃ and the rotating speed is 20r/min; the film blowing temperature is 130 ℃, 150 ℃, 175 ℃, 170 ℃ and the rotating speed is 35r/min respectively.
Performance test
The PBAT master batches prepared in examples and comparative examples were melted by a screw extruder having an aspect ratio of 30:1, extruded, and blow molded into films, to prepare PBAT preservative films, and then the properties of the PBAT preservative films were measured according to the following methods, and the measurement results were recorded in table 2.
1. Water vapor transmission rate: detecting according to GB/T2653-2010 infrared detector method for measuring water vapor transmittance of plastic films and sheets, wherein the detected humidity is 80% RH;
2. tensile strength: determination of the tensile Properties of plastics according to GB/T1040.3-2006 section 3: testing conditions of the film and the sheet;
3. stagnant water volume: winding the prepared preservative film on a refrigerator fruit and vegetable box with tightness, fixing the preservative film by using a rope, tightening the film surface of the preservative film, placing 400g of spinach in the fruit and vegetable box, placing the preservative film in a refrigerator at 5 ℃ for 30min, observing the conditions of infiltration, fogging, water condensation and water dripping on the inner surface of the preservative film, adjusting the measurement time, taking down the preservative film, placing the preservative film in a small beaker with the weight (W1), weighing (marked as W1), taking out the preservative film, placing the preservative film on filter paper to suck the moisture on the surface of the preservative film, placing the preservative film in the small beaker for weighing (marked as W2), and calculating the water retention according to the following conditions: stagnant water (g) =w1-W2;
4. selecting celery with uniform size and bright and similar surface color, mechanical damage to objects and pest infestation, packaging into preservative film, sealing 500g each, parallelizing each example or comparative example for 3 times, storing at normal temperature of 0-12 ℃, measuring the weight of the celery after 21 days, and detecting the weight loss rate.
Table 2 performance test of PBAT preservative film
In combination with the contents of table 2 and examples 1-3, the super absorbent resin and porous silica are adopted as the moisture absorption materials in examples 1-3, so that the water vapor generated by fruits and vegetables is absorbed into the preservative film, the water retention in the preservative film is reduced, the weight loss rate of the fruits and vegetables is reduced, and the shelf life is prolonged.
In examples 4 and 5, as compared with example 1, the water vapor transmission rate of the preservative film was decreased, the amount of stagnant water was increased, the weight loss rate was increased, the anti-fog effect on the inner surface of the preservative film was decreased, and the preservative ability was decreased, respectively, by using the super absorbent resin and porous silica as the moisture absorbing materials.
In example 6, the porous silica was pretreated with magnesium oxide or the like, and the water vapor transmission rate of the preservative film prepared in example 6 was increased, the amount of stagnant water was reduced, and the anti-fogging and preservative effects were enhanced, as compared with example 1.
In example 7, compared with example 6, when the porous silica is pretreated, no magnesium oxide is added, and the water vapor transmittance, tensile strength and water retention amount of the preservative film in example 7 are similar to those of example 6, but the weight loss rate of celery is increased, which indicates that the magnesium oxide can improve the preservative capability of fruits and vegetables.
In example 8, the organic porous material was further pretreated as compared with example 6, and it is shown in table 2 that the water vapor transmission rate of the preservative film prepared in example 8 was greater than that of example 6,
in example 9, although the amount of stagnant water on the inner surface of the preservative film was reduced as compared with example 8 by adding the defogging agent, the water vapor transmittance, tensile strength and weight loss rate of celery were not greatly changed as compared with example 8, which means that the use of the perfluoroalkyl amide as the defogging agent only reduced the condensation of water vapor on the inner surface of the preservative film, prevented the fogging, and prevented the water vapor from dropping on the fruits and vegetables.
In example 10, the defogging agent was prepared by using the loofah sponge fiber and graphene oxide dispersion liquid, and compared with example 8, the transmittance of the preservative film to water vapor was increased, the tensile strength was increased, the water retention was reduced, and the preservation ability of fruits and vegetables was also enhanced.
The moisture absorption material is not added in the comparative example 1, the organic porous material is not added in the comparative example 2, and compared with the example 1, the preservative films prepared in the comparative examples 1 and 2 have poor moisture permeability, large water retention and reduced preservation capacity.
The comparative example 3 is a degradable preservative film prepared by the prior art, and the preservative film has large water retention, poor moisture permeability and inferior preservative capability compared with the example 1.
Comparative example 4 is an anti-fog preservative film, which can form a water film on the inner surface without fogging, but has high water vapor transmittance, large water stagnation and easy dripping in fruits and vegetables, so that the preservation effect is weakened.
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 (8)
1. The PBAT master batch is characterized by comprising the following raw materials in parts by weight: 20-50 parts of PBAT, 0.5-2 parts of lubricant, 0.5-2 parts of antioxidant, 2-3 parts of compatilizer, 5-15 parts of inorganic micro powder, 5-10 parts of hygroscopic material, 5-10 parts of organic porous material and 0.6-2.2 parts of mildew preventive;
the moisture absorption material comprises super absorbent resin and porous silicon dioxide, wherein the mass ratio of the super absorbent resin to the porous silicon dioxide is 0.3-0.5:1;
the preparation method of the organic porous material comprises the following steps: dimethyl sulfoxide is used as a solvent, a solution of octanediamine and trimesic aldehyde with the concentration of 0.15mol/L is prepared, wherein the molar ratio of the octanediamine to the trimesic aldehyde is 3:2, 2.5 mu L of octanoic acid is added as a catalyst, the mixture is stood still to obtain milky gel, and ethanol solutions with the mass fractions of 20%, 40%, 60%, 80% and 99.7% are respectively used for carrying out gradient solvent replacement, the total solvent replacement is carried out for 2d, the mixture is subjected to vacuum freeze drying for 24h, and the mixture is crushed to obtain the organic porous material with the particle size of 0.02 mm.
2. The PBAT master batch of claim 1, wherein the porous silica is pretreated by:
mixing magnesium oxide and porous silicon dioxide, adding sodium hydroxide, crystalline aluminum chloride and distilled water, heating to 110-120deg.C, stirring for 8-10 hr, filtering, and oven drying.
3. The PBAT master batch as claimed in claim 2, wherein the porous silica is pretreated by the following raw materials in parts by weight: 1.5 to 3.5 parts of magnesium oxide, 5 to 10 parts of porous silicon dioxide, 1 to 2 parts of sodium hydroxide, 2 to 4 parts of crystalline aluminum chloride and 25 to 50 parts of distilled water.
4. The PBAT master batch of claim 1, wherein the organic porous material is pretreated by:
placing the organic porous material into a lithium chloride solution with the mass fraction of 25-30%, heating to 60-80 ℃, stirring for 80-90min, vacuum filtering, drying, and grinding, wherein the mass ratio of the organic porous material to the lithium chloride solution is 1:13-15.
5. The PBAT master batch according to claim 1, further comprising 3-7 parts of a defogging agent, wherein the defogging agent is prepared by circularly dipping a graphene oxide dispersion liquid after pickling loofah sponge fibers, and then drying, reducing and washing.
6. The PBAT master batch according to claim 1, wherein the inorganic micro powder is at least one selected from the group consisting of calcium carbonate powder, talc powder, quartz powder, montmorillonite powder, gypsum powder.
7. The method for preparing the PBAT master batch as claimed in any one of claims 1 to 6, which comprises the following steps:
weighing the raw materials according to the raw material dosage of the PBAT master batch, uniformly mixing, melting, extruding and granulating.
8. The PBAT preservative film is characterized by comprising the following raw materials in parts by weight: 40-60 parts of the PBAT masterbatch according to any one of claims 1-6, 10-20 parts of PLA, 0.1-0.5 part of an antioxidant, 0.2-1 part of a plasticizer, 0.2-1 part of a chain extender, and 10-20 parts of a coupling modified nano calcium carbonate.
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