CN116589836A - Green safe biodegradable material and preparation method and application thereof - Google Patents

Green safe biodegradable material and preparation method and application thereof Download PDF

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Publication number
CN116589836A
CN116589836A CN202310854171.XA CN202310854171A CN116589836A CN 116589836 A CN116589836 A CN 116589836A CN 202310854171 A CN202310854171 A CN 202310854171A CN 116589836 A CN116589836 A CN 116589836A
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parts
poly
natural product
biodegradable material
biodegradable
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刘琪
何文清
刘家磊
董闫闫
刘勤
张茂林
崔吉晓
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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Priority to CN202310854171.XA priority Critical patent/CN116589836A/en
Publication of CN116589836A publication Critical patent/CN116589836A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
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    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
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    • C08K9/10—Encapsulated ingredients
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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Polymers & Plastics (AREA)
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Abstract

The invention provides a green safe biodegradable material, a preparation method and application thereof, and relates to the technical field of biodegradable materials. The invention provides a green safe biodegradable material, which comprises the following preparation raw materials in parts by weight: 68-99.998 parts of biodegradable polyester; 0-10 parts of inorganic filler; 0.001-4 parts of natural product ultraviolet stabilizer; 0.001-4 parts of natural product antioxidant; 0-2 parts of a compatilizer; 0-2 parts of plasticizer; 0-2 parts of a lubricant; 0-8 parts of color masterbatch. The green safe biodegradable material provided by the invention not only has higher mechanical property, barrier property and ageing resistance, but also can prevent the application of toxic reagents in the preparation process of the biodegradable material, and avoid or reduce secondary pollution generated in the use process.

Description

Green safe biodegradable material and preparation method and application thereof
Technical Field
The invention relates to the technical field of biodegradable materials, in particular to a green safe biodegradable material and a preparation method and application thereof.
Background
The biodegradable plastic has good mechanical property, high ductility and elongation at break, and good biodegradability, and can be decomposed into carbon dioxide and water by microorganisms in the environment after being used, so that environmental pollution can be effectively avoided. Therefore, biodegradable plastics are regarded as ideal materials for replacing conventional plastics polyethylene and polystyrene and are a research hotspot in the field of materials.
The China is a large agricultural country, and the mulching film is an important agricultural production data in China. The plastic film has large coverage area and wide application range, and plays an important role in increasing crop yield, improving crop quality, enriching agricultural product supply structures and the like. As the mulching film is exposed outdoors for a long time, and is subjected to sun and rain exposure, the mulching film is extremely easy to age and become brittle, so that the elongation at break of the mulching film is rapidly reduced, and the mulching film is mainly shown as a hole and crack to fail in appearance change, so that the service life requirement of a crop planting period cannot be met, and the expected functional effect of the mulching film cannot be achieved. The expected service life of the biodegradable mulching film is generally 1-6 months, if ultraviolet aging resistance and oxidation resistance prevention are not carried out, the biodegradable mulching film can be broken and lose efficacy in the planting period, and the mechanical property, the barrier property, the grass prevention effect and the like of the mulching film are greatly influenced.
The application of the ultraviolet stabilizer can effectively relieve the problem of premature degradation of the biodegradable material due to aging in the use process, and the prior art mainly adds inorganic ultraviolet stabilizer (mostly metal oxide or ceramic powder, such as nano TiO) 2 ZnO, etc.), and an antioxidant (amines, phenols, thioesters, phosphites, etc.) may be added in some cases. For example, patents CN114851672A, CN114149667a and CN115386210a. However, inorganic ultraviolet stabilizer materials in the prior art are easy to agglomerate and change color in the preparation process, and the ultraviolet absorption effect is seriously affected; organic ultraviolet stabilizer materials cannot realize full spectrum sun protection, and some small molecules have the problems of toxicity, poor thermal stability, easy migration, easy decomposition and the like, and can not well solve the problem of premature degradation. In addition, because biodegradable plastics degrade during use, for example, biodegradable mulch films degrade in situ in the soil environment of a farmland, additives can be released into the soil and pose an environmental risk.
Disclosure of Invention
The invention aims to provide a green safe biodegradable material, a preparation method and application thereof, and the green safe biodegradable material provided by the invention not only has higher mechanical property, barrier property and ageing resistance, but also can prevent the application of toxic reagents in the preparation process of the biodegradable material, and avoid or reduce secondary pollution generated in the use process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a green safe biodegradable material, which comprises the following preparation raw materials in parts by weight:
68-99.998 parts of biodegradable polyester;
0-10 parts of inorganic filler;
0.001-4 parts of natural product ultraviolet stabilizer;
0.001-4 parts of natural product antioxidant;
0-2 parts of a compatilizer;
0-2 parts of plasticizer;
0-2 parts of a lubricant;
0-8 parts of color masterbatch.
Preferably, the natural product uv stabilizer comprises a uv resistant active; the ultraviolet resistant active substance comprises one or more of baicalin, punicalagin, rutin, shikonin, emodin, curcumin, berberine, chlorogenic acid, imperatorin and isoeuro Hu Suzhong.
Preferably, the natural product uv stabilizer further comprises a carrier supporting the uv resistant active substance or a capsule wall coating the uv resistant active substance.
Preferably, the natural product antioxidant comprises an antioxidant active; the antioxidant active substance comprises one or more of lipoic acid, vitamin E, vitamin C, beta-carotene, tea polyphenol, oryzanol, quercetin, ferulic acid, N-acetylcysteine, glutathione, resveratrol, mangiferin, carboxymethyl chitosan, banana male flower extract, pomegranate seed extract, grape seed extract, sea buckthorn seed extract and rosmarinic acid.
Preferably, the natural product antioxidant further comprises a carrier supporting the antioxidant active substance or a capsule wall coating the antioxidant active substance.
Preferably, the carrier is an inorganic carrier; the preparation raw materials of the capsule wall comprise one or more of chitosan, cellulose, modified cellulose, sodium alginate, liposome, natural polysaccharide, zein, gelatin, agar, acacia, lemon oil and hydroxy cyclodextrin.
Preferably, the biodegradable polyester comprises one or more of poly (adipic acid)/poly (butylene terephthalate), poly (butylene succinate), poly (lactic acid), poly (propylene carbonate), poly (hydroxy alkanoate), poly (epsilon-caprolactone), poly (glycolic acid), poly (vinyl alcohol), poly (beta-hydroxybutyrate), poly (hydroxy valerate), poly (hydroxy butyrate) valerate and poly (glycolic acid).
The invention provides a preparation method of the green safe biodegradable material, which comprises the following steps:
mixing the preparation raw materials of the green safe biodegradable material to obtain a mixed material;
and processing and forming the mixed material to obtain the green safe biodegradable material.
The invention provides a preparation method of the green safe biodegradable material, which comprises the following steps:
mixing part of biodegradable polyester with other preparation raw materials of the green safe biodegradable material to obtain a primary mixed material;
extruding and granulating the primary mixed material to obtain biodegradable polyester master batch;
and mixing the biodegradable polyester master batch with the rest biodegradable polyester, and molding to obtain the green safe biodegradable material.
The invention provides an application of the green safe biodegradable material in packaging or agricultural plastics.
The invention provides a green safe biodegradable material, wherein the natural product ultraviolet stabilizer and the natural product antioxidant are natural active substances extracted from plants, and the material has the advantages of safety, no toxicity or low toxicity, no pollution, small environmental impact and the like. Therefore, the natural product ultraviolet stabilizer is adopted to replace the traditional chemical ultraviolet stabilizer product, and the natural product antioxidant is adopted to replace the traditional chemical antioxidant product, so that the green and safe biodegradable material is prepared, the mechanical property, the barrier property and the ageing resistance of the biodegradable material can be improved, the application of toxic reagents in the preparation process of the biodegradable material can be stopped, and the secondary pollution generated in the use process can be avoided or reduced.
Compared with the prior art, the invention has the beneficial effects that:
the green safe biodegradable material provided by the invention adopts biodegradable polyester as a raw material, and a natural product ultraviolet stabilizer and a natural product antioxidant are used as main functional auxiliary agents, so that the material is green and safe in the processing and using processes, and can be used in the fields of food packaging, agricultural mulching films and the like;
the green safe biodegradable material provided by the invention can be completely degraded, has no chemical additive residue, no secondary pollution and no recovery, can effectively reduce or eliminate environmental secondary pollutants generated by degradation of the biodegradable material in natural environment, and improves living or agricultural environment;
the green safe biodegradable material provided by the invention has excellent ultraviolet aging resistance and oxidation resistance, wherein after the film product is artificially aged by 100 h or 200 h, the film product can still keep good mechanical properties and has good weather resistance;
the green safe biodegradable material provided by the invention has excellent mechanical property and barrier property, and the film product can meet the requirements of GB/T35795-2017 'full biodegradable agricultural ground covering film' and GB/T10004-2008 'packaging plastic composite film bag dry-process compounding and extrusion compounding', and can be used in the fields of food packaging, agricultural mulching films and the like.
Drawings
FIG. 1 is a graph showing the effect of the biodegradable materials prepared in example 1 and comparative example 1 on the biomass of earthworms.
Detailed Description
The invention provides a green safe biodegradable material, which comprises the following preparation raw materials in parts by weight:
68-99.998 parts of biodegradable polyester;
0-10 parts of inorganic filler;
0.001-4 parts of natural product ultraviolet stabilizer;
0.001-4 parts of natural product antioxidant;
0-2 parts of a compatilizer;
0-2 parts of plasticizer;
0-2 parts of a lubricant;
0-8 parts of color masterbatch.
The green safe biodegradable material provided by the invention comprises 68-99.998 parts by weight of biodegradable polyester, preferably 94.6-98 parts by weight, and more preferably 95-97.7 parts by weight. In the present invention, the biodegradable polyester preferably includes one or more of poly (adipic acid)/poly (butylene terephthalate) (PBAT), poly (butylene succinate) (PBS), poly (lactic acid) (PLA), poly (propylene carbonate) (PPC), poly (hydroxyalkanoate) (PHA), poly (epsilon-caprolactone) (PCL), poly (glycolic acid) (PGA), poly (vinyl alcohol) (PVA), poly (beta-hydroxybutyrate) (PHB), poly (hydroxyvalerate) (PHV), poly (hydroxybutyrate-valerate) (PHBV), and poly (glycolic acid) (PGA), more preferably one or more of PBAT, PLA, and PPC.
The green safe biodegradable material provided by the invention comprises 0-10 parts by weight of inorganic filler, preferably 0.4-2 parts by weight, and more preferably 1-1.5 parts by weight of biodegradable polyester. In the present invention, the size range of the inorganic filler is preferably 100nm to 2 μm. In the present invention, the inorganic filler preferably includes one or more of talc, calcium carbonate, calcium sulfate, kaolin, montmorillonite, diatomaceous earth, alumina, titanium oxide, magnesium hydroxide, silica, mica, and zinc oxide, more preferably talc, silica, or calcium carbonate.
The green safe biodegradable material provided by the invention comprises, by weight, 0.001-4 parts of natural product ultraviolet stabilizer, preferably 0.3-1 part, and more preferably 0.5-0.8 part. In the present invention, the natural product uv stabilizer comprises a uv resistant active substance; the ultraviolet resistant active substance preferably comprises one or more of baicalin, punicalagin, rutin, shikonin, emodin, curcumin, berberine, chlorogenic acid, imperatorin and isoeuclidean Hu Suzhong, more preferably one or more of rutin, shikonin, curcumin, berberine and baicalin. In the invention, when the natural product ultraviolet stabilizer is a mixture of curcumin and berberine, the mass ratio of the curcumin to the berberine is preferably 1:1; when the natural product ultraviolet stabilizer is a mixture of baicalin and rutin, the mass ratio of the baicalin to the rutin is preferably 1:1.
In the present invention, the natural product uv stabilizer preferably further comprises a carrier supporting the uv-resistant active substance or a capsule wall coating the uv-resistant active substance. In the present invention, the carrier is preferably an inorganic carrier. In the present invention, the inorganic carrier preferably includes activated carbon, silica, nano silica, montmorillonite, biochar or attapulgite. In the invention, the preparation raw materials of the capsule wall preferably comprise one or more of chitosan, cellulose, modified cellulose, sodium alginate, liposome, natural polysaccharide, zein, gelatin, tannic acid, agar, acacia, lemon oil and hydroxy cyclodextrin. In the present invention, when the natural product uv stabilizer includes a capsule wall coating the uv resistant active substance, the natural product uv stabilizer is a microcapsule; the method of preparing the natural product ultraviolet stabilizer into microcapsules preferably comprises interfacial polymerization, in-situ polymerization or spray drying.
In the present invention, when the natural product uv stabilizer further includes a carrier supporting the uv-resistant active substance, the mass of the uv-resistant active substance is preferably 10 to 90% of the total mass of the natural product uv stabilizer, more preferably 20 to 60%. In the present invention, when the natural product uv stabilizer further includes a capsule wall coating the uv-resistant active material, the mass of the uv-resistant active material is preferably 10 to 90% of the total mass of the natural product uv stabilizer, and more preferably 30 to 80%.
The green safe biodegradable material provided by the invention comprises, by weight, 0.001-4 parts of a natural product antioxidant, preferably 0.3-1 part, and more preferably 0.5-0.8 part. In the present invention, the natural product antioxidant comprises an antioxidant active; the antioxidant active substance preferably comprises one or more of lipoic acid, vitamin E, vitamin C, beta carotene, tea polyphenol, oryzanol, quercetin, ferulic acid, N-acetylcysteine, glutathione, resveratrol, mangiferin, carboxymethyl chitosan, banana male flower extract, pomegranate seed extract, grape seed extract, sea buckthorn seed extract and rosmarinic acid, more preferably one or more of tea polyphenol, N-acetylcysteine, ferulic acid, carboxymethyl chitosan, quercetin and resveratrol. In the invention, when the natural product antioxidant is a mixture of resveratrol and ferulic acid, the mass ratio of resveratrol to ferulic acid is preferably 1:1; when the natural product antioxidant is a mixture of vitamin E and oryzanol, the mass ratio of the vitamin E to oryzanol is preferably 1:1; when the natural product antioxidant is a mixture of grape seed extract and ferulic acid, the mass ratio of grape seed extract to ferulic acid is preferably 1:1.
In the present invention, the natural product antioxidant preferably further comprises a carrier supporting the antioxidant active substance or a capsule wall coating the antioxidant active substance. In the present invention, the carrier is preferably an inorganic carrier. In the present invention, the inorganic carrier preferably includes activated carbon, silica, nano silica, montmorillonite, biochar or attapulgite. In the invention, the preparation raw materials of the capsule wall preferably comprise one or more of chitosan, cellulose, modified cellulose, sodium alginate, liposome, natural polysaccharide, zein, gelatin, tannic acid, agar, acacia, lemon oil and hydroxy cyclodextrin. In the present invention, when the natural product antioxidant includes a capsule wall coating the antioxidant active substance, the natural product antioxidant is a microcapsule; the method of preparing the natural product antioxidant into microcapsules preferably comprises interfacial polymerization, in situ polymerization or spray drying.
In the invention, when the natural product antioxidant further comprises a carrier for supporting the antioxidant active substance, the mass of the antioxidant active substance is preferably 10-90% of the total mass of the natural product antioxidant, and more preferably 20-60%. In the invention, when the natural product antioxidant further comprises a capsule wall coating the antioxidant active substance, the mass of the antioxidant active substance is preferably 10-90% of the total mass of the natural product antioxidant, and more preferably 30-80%.
The green safe biodegradable material provided by the invention comprises 0-2 parts by weight of a compatilizer, preferably 0.4-0.5 parts by weight of the biodegradable polyester. In the present invention, the compatibilizing agent preferably includes one or more of a non-reactive compatibilizing agent and a reactive compatibilizing agent; the non-reactive compatibilizer preferably comprises one or more of Ethylene Acrylic Acid (EAA), ethylene Ethyl Acrylate (EEA), and ethylene vinyl acetate copolymer (EVA); the reactive compatibilizer preferably comprises one or more of an anhydride compatibilizer, an epoxy compatibilizer, an imine compatibilizer, a carboxylic acid compatibilizer, an oxazoline compatibilizer and an isocyanate compatibilizer, and more preferably maleic anhydride, maleic anhydride grafted polylactic acid or an epoxy compatibilizer. In the present invention, when the compatibilizer is a mixture of maleic anhydride grafted polylactic acid and ethylene-vinyl acetate copolymer (EVA), the mass ratio of the maleic anhydride grafted polylactic acid to the ethylene-vinyl acetate copolymer (EVA) is preferably 1:1.
The green safe biodegradable material provided by the invention comprises 0-2 parts of plasticizer, preferably 0.3-1 part of plasticizer, by weight of the biodegradable polyester. In the present invention, the plasticizer preferably includes one or more of a citrate plasticizer, an epoxy plasticizer, a trioctyl trimellitate plasticizer, and a di (2-propylheptyl) phthalate plasticizer. In the present invention, the citrate plasticizer preferably includes one or more of tributyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate, more preferably tributyl citrate; the epoxy plasticizer preferably comprises one or more of epoxidized soybean oil and octyl 9, 10-epoxy stearate.
The green safe biodegradable material provided by the invention comprises 0-2 parts by weight of lubricant, preferably 0.4-1.2 parts by weight, and more preferably 0.5-0.6 parts by weight of biodegradable polyester. In the present invention, the lubricant preferably includes one or more of fatty acid amide type lubricants, fatty acid ester type lubricants, bis stearamide (EBS) and its derivative lubricants, alkane type lubricants, silicone type lubricants, talc, diatomaceous earth and silica. In the present invention, the fatty acid amide-based lubricant preferably includes one or more of erucamide and oleamide; when the fatty acid amide-based lubricant is a mixture of erucamide and oleamide, the mass ratio of the erucamide to oleamide is preferably 1:1. In the present invention, the paraffinic lubricant is preferably a paraffinic lubricant. In the present invention, the lubricant is preferably a mixture of bis stearamide (EBS) and erucamide; the mass ratio of the bis-stearamide (EBS) to the erucamide is preferably 2:1.
The green safe biodegradable material provided by the invention comprises 0-8 parts of color masterbatch, preferably 2.5-3 parts of color masterbatch, calculated by weight of the biodegradable polyester. In the present invention, the color master batch is preferably carbon black or a color master batch of other colors. In the present invention, the color master does not contain polyolefin or other non-biodegradable polymer.
The invention provides a preparation method of the green safe biodegradable material, which comprises the following steps:
mixing the preparation raw materials of the green safe biodegradable material to obtain a mixed material;
and processing and forming the mixed material to obtain the green safe biodegradable material.
The preparation raw materials of the green safe biodegradable material are mixed to obtain a mixed material. In the present invention, the biodegradable polyester is preferably dried before being mixed with other preparation raw materials. In the invention, the drying temperature is preferably 20-40 ℃, and the water content of the obtained dried biodegradable polyester is preferably lower than 0.5%, more preferably 0.2%. In the present invention, the mixing is preferably performed in a high-speed mixer.
After the mixed material is obtained, the mixed material is processed and molded to obtain the green safe biodegradable material. In the present invention, the process molding preferably includes film processing, injection molding, or compression molding. In the present invention, the film processing preferably includes extrusion granulation and film formation performed sequentially; the film formation preferably comprises blown film or cast film. In the present invention, the extrusion granulation is preferably performed in an extrusion molding apparatus, and particularly preferably in a twin-screw extruder. In the present invention, the temperature of the extrusion granulation is preferably 130 to 195 ℃, more preferably 160 to 185 ℃. In the present invention, the temperature of the blown film is preferably 130 to 195 ℃, more preferably 140 to 165 ℃.
The invention provides another preparation method of the green safe biodegradable material, which comprises the following steps:
mixing part of biodegradable polyester with other preparation raw materials of the green safe biodegradable material to obtain a primary mixed material;
extruding and granulating the primary mixed material to obtain biodegradable polyester master batch;
and mixing the biodegradable polyester master batch with the rest biodegradable polyester, and molding to obtain the green safe biodegradable material.
The invention mixes partial biodegradable polyester with other preparation raw materials of the green safe biodegradable material to obtain a primary mixed material. In the present invention, the biodegradable polyester is preferably dried before use. In the present invention, the drying temperature is preferably 20 to 40 ℃, and the water content of the obtained dried biodegradable polyester is preferably less than 0.5%, more preferably 0.2%. In the present invention, the mixing is preferably performed in a high-speed mixer. In the invention, the mass of the partially biodegradable polyester is preferably 5-80% of the total mass of the biodegradable polyester, and more preferably 28-49%.
After the primary mixed material is obtained, the primary mixed material is extruded and granulated to obtain the biodegradable polyester master batch. In the present invention, the extrusion granulation is preferably performed in an extrusion molding apparatus, and particularly preferably in a twin-screw extruder. In the present invention, the temperature of the extrusion granulation is preferably 130 to 195 ℃, more preferably 160 to 185 ℃.
After the biodegradable polyester master batch is obtained, the biodegradable polyester master batch and the residual biodegradable polyester are mixed and molded to obtain the green safe biodegradable material. In the present invention, the molding preferably includes film forming, injection molding or compression molding. In the present invention, the film formation preferably includes a blown film or a cast film. In the present invention, the temperature of the blown film is preferably 130 to 195 ℃, more preferably 140 to 165 ℃.
In a specific embodiment of the present invention, the green safe biodegradable material is preferably in a film form. The thickness of the green safe biodegradable film material prepared by the invention is preferably 4-100 mu m.
The invention provides an application of the green safe biodegradable material in packaging or agricultural plastics. In the present invention, the package preferably comprises a food package; the agricultural plastic preferably comprises an agricultural mulching film, a vine hanging rope or a fruit bagging.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
96.9 parts of poly (adipic acid)/butylene terephthalate (PBAT);
1.5 parts of inorganic filler;
0.5 part of natural product ultraviolet stabilizer;
0.5 part of natural product antioxidant;
0.6 parts of lubricant;
the inorganic filler is talcum powder; the natural product ultraviolet stabilizer is rutin; the natural product antioxidant is tea polyphenol; the lubricant is erucamide.
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) Weighing 96.9 parts of poly (adipic acid)/butylene terephthalate, and drying until the water content is 0.2%;
(2) 1.5 parts of inorganic filler, 0.5 part of natural product ultraviolet stabilizer, 0.5 part of natural product antioxidant and 0.6 part of lubricant are weighed and mixed with 26.9 parts of poly (adipic acid)/butylene terephthalate, and the mixture is stirred uniformly by a high-speed mixer to obtain a primary mixed material; transferring the obtained primary mixed material into a double-screw extruder, extruding and granulating the primary mixed material to obtain biodegradable polyester master batch; then mixing with 70 parts of poly (adipic acid)/butylene terephthalate, and blow molding to form a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 170-185 ℃ (the temperature of one area of the double-screw extruder is 170 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Example 2
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
89.7 parts of poly (adipic acid)/butylene terephthalate (PBAT);
8 parts of polylactic acid (PLA);
0.5 part of natural product ultraviolet stabilizer;
0.5 part of natural product antioxidant;
0.5 parts of compatilizer;
0.3 parts of plasticizer;
0.5 parts of lubricant;
the natural product ultraviolet stabilizer is baicalin; the natural product antioxidant is a mixture of resveratrol and ferulic acid according to a mass ratio of 1:1; the compatilizer is a mixture of maleic anhydride grafted polylactic acid and ethylene-vinyl acetate copolymer (EVA) according to a mass ratio of 1:1; the plasticizer is tributyl citrate; the lubricant is oleamide.
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) Weighing 89.7 parts of poly (adipic acid)/poly (butylene terephthalate) and 8 parts of polylactic acid, and respectively drying until the water content is 0.2%;
(2) Weighing 0.5 part of natural product ultraviolet stabilizer, 0.5 part of natural product antioxidant, 0.5 part of compatilizer, 0.3 part of plasticizer, 0.5 part of lubricant and biodegradable polyester (39.7 parts of poly (adipic acid)/butylene terephthalate and 8 parts of polylactic acid), mixing uniformly by a high-speed mixer, and obtaining a primary mixed material; transferring the obtained primary mixed material into a double-screw extruder, extruding and granulating the primary mixed material to obtain biodegradable polyester master batch; then mixing with 50 parts of poly (adipic acid)/butylene terephthalate, and blow molding to form a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 175-190 ℃ (the temperature of one area of the double-screw extruder is 175 ℃ and the temperature of a die head is 190 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Example 3
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
88 parts of poly (adipic acid)/butylene terephthalate (PBAT);
5 Parts of Polypropylene Carbonate (PPC);
5 parts of polylactic acid (PLA);
0.4 parts of inorganic filler;
0.3 parts of natural product ultraviolet stabilizer;
0.3 parts of natural product antioxidant;
0.4 parts of compatilizer;
0.6 parts of lubricant;
the inorganic filler is calcium carbonate; the natural product ultraviolet stabilizer is a mixture of curcumin and berberine according to a mass ratio of 1:1; the natural product antioxidant is quercetin; the compatilizer is epoxy resin; the lubricant is bis-stearamide (EBS).
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) 88 parts of poly (adipic acid)/poly (butylene terephthalate), 5 parts of poly (propylene carbonate) and 5 parts of polylactic acid are weighed and dried respectively until the water content is 0.2%;
(2) Weighing 0.4 part of inorganic filler, 0.3 part of natural product ultraviolet stabilizer, 0.3 part of natural product antioxidant, 0.4 part of compatilizer and 0.6 part of lubricant, mixing with biodegradable polyester (poly (adipic acid)/butylene terephthalate, poly (propylene carbonate) and polylactic acid), and uniformly stirring by a high-speed mixer to obtain a mixed material; transferring the obtained mixture into a double-screw extruder, extruding, granulating and blow molding the mixture into a film to obtain the green safe biodegradable film material; the temperature of the extrusion granulation is (the temperature of a zone of a double-screw extruder is 175 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 145-155 ℃ (the temperature of a first area of a film blowing unit is 145 ℃ and the temperature of a die head is 155 ℃).
Example 4
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
94.8 parts of poly (adipic acid)/butylene terephthalate (PBAT);
2 parts of inorganic filler;
1 part of natural product ultraviolet stabilizer (microcapsule);
1 part of natural product antioxidant (microcapsule);
1.2 parts of lubricant;
the inorganic filler is talcum powder;
the natural product ultraviolet stabilizer (microcapsule) is microcapsule with total weight content of baicalin and rutin of 50% (the mass ratio of the baicalin to the rutin is 1:1), and the preparation method is as follows: uniformly mixing 10g of zein with 50mL of ethanol under stirring, and regulating the pH to 11 to obtain a zein solution; uniformly mixing 5g of baicalin and 5g of rutin, dissolving in the zein solution, adjusting the temperature to 40 ℃ and drying and curing to obtain the natural product ultraviolet stabilizer (microcapsule); the natural product antioxidant (microcapsule) is microcapsule with total vitamin E and oryzanol content of 50% (the mass ratio of the vitamin E to oryzanol is 1:1), and the preparation method is as follows: mixing 5g of vitamin E and 5g of oryzanol, dissolving in 200mL of gelatin water solution with concentration of 5wt%, adding 0.5g of tannic acid, adjusting pH to 9, reacting for 48 hours, freeze-drying, crushing, and sieving with a 5000-mesh sieve to obtain the natural product antioxidant (microcapsule);
The lubricant is erucamide;
the preparation method of the green safe biodegradable film material comprises the following steps:
(1) Weighing 94.8 parts of poly (adipic acid)/butylene terephthalate, and drying until the water content is 0.2%;
(2) Weighing 2 parts of inorganic filler, 1 part of natural product ultraviolet stabilizer (microcapsule), 1 part of natural product antioxidant (microcapsule), 1.2 parts of lubricant and poly (adipic acid)/butylene terephthalate, and uniformly stirring by a high-speed mixer to obtain a mixed material; transferring the obtained mixture into a double-screw extruder, extruding, granulating and blow molding the mixture into a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 175-185 ℃ (the temperature of one area of the double-screw extruder is 175 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 135-145 ℃ (the temperature of a first area of a film blowing unit is 135 ℃ and the temperature of a die head is 145 ℃).
Example 5
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
90 parts of poly (adipic acid)/butylene terephthalate (PBAT);
5 parts of polylactic acid (PLA);
0.4 parts of compatilizer;
0.8 part of natural product ultraviolet stabilizer (montmorillonite load);
0.8 part of natural product antioxidant (montmorillonite load);
0.5 parts of lubricant;
2.5 parts of color masterbatch;
the natural product ultraviolet stabilizer (montmorillonite load) is chlorogenic acid loaded on montmorillonite, the mass content of the chlorogenic acid is 50% of the total mass of the natural product ultraviolet stabilizer (montmorillonite load), and the preparation method comprises the following steps: dissolving 2g of chlorogenic acid with 20mL of ethanol, adding 2g of montmorillonite, stirring, grinding and drying to obtain the natural product ultraviolet stabilizer (montmorillonite load);
the natural product antioxidant (montmorillonite load) is grape seed extract and ferulic acid (the mass ratio is 1:1) loaded on montmorillonite, the mass content of the grape seed extract and the ferulic acid is 50% of the total mass of the natural product antioxidant (montmorillonite load), and the preparation method comprises the following steps: dissolving 1g of grape seed extract and 1g of ferulic acid with 20mL of ethanol, adding 2g of montmorillonite, stirring, grinding and drying to obtain the natural product antioxidant (montmorillonite load); the compatilizer is maleic anhydride; the lubricant is a mixture of bis-stearamide (EBS) and erucamide according to a mass ratio of 2:1; the color masterbatch is carbon black and does not contain polyolefin or other non-biodegradable polyesters.
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) Weighing 90 parts of poly (adipic acid)/poly (butylene terephthalate) and 5 parts of polylactic acid, and respectively drying until the water content is 0.2%;
(2) Weighing 0.4 part of compatilizer, 0.8 part of natural product ultraviolet stabilizer (montmorillonite load), 0.8 part of natural product antioxidant (montmorillonite load), 0.5 part of lubricant and 2.5 parts of color masterbatch, mixing with poly (adipic acid)/poly (butylene terephthalate) and poly (lactic acid), and uniformly stirring by a high-speed mixer to obtain a mixed material; transferring the obtained mixture into a double-screw extruder, extruding, granulating and blow molding the mixture into a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 175-190 ℃ (the temperature of one area of the double-screw extruder is 175 ℃ and the temperature of a die head is 190 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Example 6
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
94.6 parts of poly (adipic acid)/butylene terephthalate (PBAT);
1 part of inorganic filler;
0.5 part of natural product ultraviolet stabilizer;
0.5 part of natural product antioxidant;
0.4 parts of lubricant;
3 parts of color masterbatch;
the inorganic filler is silicon dioxide; the natural product ultraviolet stabilizer is shikonin; the natural product antioxidant is N-acetylcysteine; the lubricant is a mixture of erucamide and oleamide according to a mass ratio of 1:1; the color masterbatch is carbon black and does not contain polyolefin or other non-biodegradable polyesters.
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) 94.6 parts of poly (adipic acid)/butylene terephthalate is weighed and dried until the water content is 0.2%;
(2) 1 part of inorganic filler, 0.5 part of natural product ultraviolet stabilizer, 0.5 part of natural product antioxidant, 0.4 part of lubricant and 3 parts of color master batch are weighed and mixed with poly (adipic acid)/butylene terephthalate, and the mixture is obtained after the mixture is stirred uniformly by a high-speed mixer; transferring the obtained mixture into a double-screw extruder, extruding, granulating and blow molding the mixture into a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 175-185 ℃ (the temperature of one area of the double-screw extruder is 175 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Example 7
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
95.9 parts of poly (adipic acid)/butylene terephthalate (PBAT);
1.5 parts of inorganic filler;
1 part of natural product ultraviolet stabilizer (microcapsule);
1 part of natural product antioxidant (microcapsule);
0.6 parts of lubricant;
the inorganic filler is talcum powder; the lubricant is erucamide.
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) The natural product ultraviolet stabilizer (microcapsule) is microcapsule with rutin mass content of 50%, and the preparation method is as follows: uniformly mixing 5g of zein with 25mL of ethanol under stirring, and regulating the pH to 11 to obtain a zein solution; dissolving 5g of rutin in the zein solution, regulating the temperature to 40 ℃ and drying and solidifying to obtain the natural product ultraviolet stabilizer (microcapsule);
(2) The natural product antioxidant (microcapsule) is a microcapsule with the mass content of tea polyphenol of 50%, and the preparation method comprises the following steps: dissolving 5g of tea polyphenol in 100mL of gelatin water solution with the concentration of 5wt%, adding 0.25g of tannic acid, adjusting the pH to 9, reacting for 48 hours, freeze-drying, crushing, and sieving with a 5000-mesh sieve to obtain the natural product antioxidant (microcapsule);
(3) Weighing 95.9 parts of poly (adipic acid)/butylene terephthalate, and drying until the water content is 0.2%;
(4) 1.5 parts of inorganic filler, 1 part of natural product ultraviolet stabilizer (microcapsule), 1 part of natural product antioxidant (microcapsule) and 0.6 part of lubricant are weighed and mixed with 25.9 parts of poly (adipic acid)/butylene terephthalate, and the mixture is stirred uniformly by a high-speed mixer to obtain a primary mixed material; transferring the obtained primary mixed material into a double-screw extruder, extruding and granulating the primary mixed material to obtain biodegradable polyester master batch; then mixing with 70 parts of poly (adipic acid)/butylene terephthalate, and blow molding to form a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 170-185 ℃ (the temperature of one area of the double-screw extruder is 170 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Example 8
The green safe biodegradable film material is prepared from the following raw materials in parts by weight:
95.9 parts of poly (adipic acid)/butylene terephthalate (PBAT);
1.5 parts of inorganic filler;
1 part of natural product ultraviolet stabilizer (montmorillonite load);
1 part of natural product antioxidant (montmorillonite load);
0.6 parts of lubricant;
the inorganic filler is talcum powder; the lubricant is erucamide.
The preparation method of the green safe biodegradable film material comprises the following steps:
(1) The natural product ultraviolet stabilizer (montmorillonite load) is rutin loaded on montmorillonite, the mass content of the rutin is 50% of the total mass of the natural product ultraviolet stabilizer (montmorillonite load), and the preparation method comprises the following steps: dissolving 2g of rutin with 20mL of ethanol, adding 2g of montmorillonite, stirring, grinding and drying to obtain the natural product ultraviolet stabilizer (montmorillonite load);
(2) The natural product antioxidant (montmorillonite load) is tea polyphenol loaded on montmorillonite, the mass content of the tea polyphenol is 50% of the total mass content of the natural product antioxidant (montmorillonite load), and the preparation method comprises the following steps: dissolving 2g of tea polyphenol with 20mL of ethanol, adding 2g of montmorillonite, stirring, grinding and drying to obtain the natural product antioxidant (montmorillonite load);
(3) Weighing 95.9 parts of poly (adipic acid)/butylene terephthalate, and drying until the water content is 0.2%;
(4) 1.5 parts of inorganic filler, 1 part of natural product ultraviolet stabilizer, 1 part of natural product antioxidant and 0.6 part of lubricant are weighed and mixed with 25.9 parts of poly (adipic acid)/butylene terephthalate, and the mixture is uniformly stirred by a high-speed mixer to obtain a primary mixed material; transferring the obtained primary mixed material into a double-screw extruder, extruding and granulating the primary mixed material to obtain biodegradable polyester master batch; then mixing with 70 parts of poly (adipic acid)/butylene terephthalate, and blow molding to form a film to obtain the green safe biodegradable film material; the temperature of extrusion granulation is 170-185 ℃ (the temperature of one area of the double-screw extruder is 170 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Comparative example 1
The same preparation as in example 1 was conducted except that the "natural product ultraviolet stabilizer" was adjusted to "2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole (UV-328)" in the raw material composition; "Natural product antioxidant" was adjusted to "B215 (a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 2:1)".
Comparative example 2
The same procedure as in example 1 was followed except that the "natural product ultraviolet stabilizer" was adjusted to "2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole (UV-328)" in the starting material composition.
Comparative example 3
The same preparation as in example 1 was carried out, except that the "natural product antioxidant" was adjusted to "B215 (a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 2:1)" in the raw material composition.
Comparative example 4
The biodegradable film material is prepared from the following raw materials in parts by weight:
97.9 parts of poly (adipic acid)/butylene terephthalate (PBAT);
1.5 parts of inorganic filler;
0.6 parts of lubricant;
the inorganic filler is talcum powder; the lubricant is erucamide;
the preparation method of the biodegradable film material comprises the following steps:
(1) Weighing 97.9 parts of poly (adipic acid)/butylene terephthalate, and drying until the water content is 0.2%;
(2) 1.5 parts of inorganic filler, 0.6 part of lubricant and 27.9 parts of poly (adipic acid)/butylene terephthalate are weighed and mixed, and a high-speed mixer is used for uniformly stirring to obtain a mixed material; transferring the obtained mixture into a double-screw extruder, extruding and granulating the mixture to obtain biodegradable polyester master batches; then mixing with 70 parts of poly (adipic acid)/butylene terephthalate, and blow molding to form a film to obtain the biodegradable film material; the temperature of extrusion granulation is 170-185 ℃ (the temperature of one area of the double-screw extruder is 170 ℃ and the temperature of a die head is 185 ℃); the temperature of the blow molding film forming is 140-150 ℃ (the temperature of a first area of a film blowing unit is 140 ℃ and the temperature of a die head is 150 ℃).
Test example 1
The performance changes of the biodegradable film materials prepared in examples 1 to 8 and comparative examples 1 to 4 before and after aging for 100 hours were detected according to national standards GB/T1040.3 and GB/T16422.2, and the thickness of the biodegradable film materials was 22.0.+ -. 0.5. Mu.m, as shown in tables 1 to 2.
Table 1 Properties before and after aging and change rates (vapor transmission amount and longitudinal stretching Properties) of each example and comparative example
TABLE 2 Properties before and after aging and change Rate (transverse tensile Properties) of examples and comparative examples
As can be seen from tables 1-2, the initial properties of the biodegradable film materials prepared in most examples are not advantageous compared with comparative example 1, but the percent decrease in properties after 100 hours of aging is relatively low, even though the mechanical properties after aging are significantly improved in some examples, such as examples 1 and 2. This demonstrates that natural product uv stabilizers and natural product antioxidants not only have the green, safe, environmental advantages over chemically synthesized uv stabilizers and antioxidants, but also have similar or superior effects on the weather resistance of biodegradable film materials as chemical additives.
Test example 2
The biodegradable film materials prepared in examples 1, 7 and 8 were tested for their performance change before and after aging for 200 hours according to national standards GB/T1040.3 and GB/T16422.2, and the thickness of the biodegradable film materials was 22.0.+ -. 0.5. Mu.m, as shown in Table 3.
TABLE 3 part of examples aging 200h before and after performance and rate of change
Table 3 shows that when the natural product ultraviolet stabilizer and the antioxidant are loaded on the inorganic carrier or the green safe biodegradable film material is prepared in the form of microcapsules (for example, example 7 and example 8), the anti-aging effect is better than that of the same type and equivalent amount of natural product ultraviolet stabilizer and antioxidant which are not loaded on the inorganic carrier or are coated by the microcapsules.
Test example 3
The results of the toxicity test of the ultraviolet stabilizer and the antioxidant residues (liquid chromatography-mass spectrometry) and the earthworms (Eisenia Fetida) of the biodegradable film materials prepared in each example and comparative example in the soil for 14 days are shown in Table 4, and the mass ratio of the biodegradable film materials to the soil is 1:100.
TABLE 4 UV stabilizer and antioxidant residues in soil for each of the examples and comparative examples and results of toxicity test on earthworms (Eisenia Fetida) for 14 days
In table 4, "-" indicates undetected; "N" means less than 5ppb and negligible.
As can be seen from the detection results in Table 4, the comparative examples 1, 2 and 3 (containing the chemically synthesized ultraviolet stabilizer and/or antioxidant) all have more than 20ppm of chemical additive residues, while the examples 1 to 8 have no or very low amounts of residues; in addition, comparative examples 1, 2 and 3 also have a higher effect on the glutathione peroxidase activity of earthworms (Eisenia Fetida) than examples 1, 2 and 3, indicating a greater effect on their anti-peroxidation ability.
FIG. 1 shows the biomass effect of the biodegradable film material prepared in example 1 and comparative example 1 on earthworms (Eisenia Fetida), according to ISO 11268. As can be seen from FIG. 1, the biomass of example 1 was not significantly changed after 14 days of culture, and the biomass of comparative example 1 was reduced by 6.5%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The green safe biodegradable material is characterized by comprising the following preparation raw materials in parts by weight:
68-99.998 parts of biodegradable polyester;
0-10 parts of inorganic filler;
0.001-4 parts of natural product ultraviolet stabilizer;
0.001-4 parts of natural product antioxidant;
0-2 parts of a compatilizer;
0-2 parts of plasticizer;
0-2 parts of a lubricant;
0-8 parts of color masterbatch.
2. The green safe biodegradable material according to claim 1, characterized in that said natural product uv stabilizer comprises a uv resistant active substance; the ultraviolet resistant active substance comprises one or more of baicalin, punicalagin, rutin, shikonin, emodin, curcumin, berberine, chlorogenic acid, imperatorin and isoeuro Hu Suzhong.
3. The green safe biodegradable material according to claim 2, characterized in that said natural product uv stabilizer further comprises a carrier supporting said uv resistant active substance or a capsule wall coating said uv resistant active substance.
4. The green safe biodegradable material according to claim 1, characterized in that said natural product antioxidant comprises an antioxidant active substance; the antioxidant active substance comprises one or more of lipoic acid, vitamin E, vitamin C, beta-carotene, tea polyphenol, oryzanol, quercetin, ferulic acid, N-acetylcysteine, glutathione, resveratrol, mangiferin, carboxymethyl chitosan, banana male flower extract, pomegranate seed extract, grape seed extract, sea buckthorn seed extract and rosmarinic acid.
5. The green safe biodegradable material according to claim 4, characterized in that said natural product antioxidant further comprises a carrier supporting said antioxidant active substance or a capsule wall coating said antioxidant active substance.
6. The green safe biodegradable material according to claim 5, characterized in that said carrier is an inorganic carrier; the preparation raw materials of the capsule wall comprise one or more of chitosan, cellulose, modified cellulose, sodium alginate, liposome, natural polysaccharide, zein, gelatin, tannic acid, agar, acacia, lemon oil and hydroxy cyclodextrin.
7. The green safety biodegradable material according to claim 1, characterized in that the biodegradable polyester comprises one or more of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (lactic acid), poly (propylene carbonate), poly (hydroxyalkanoate), poly (epsilon-caprolactone), poly (glycolic acid), poly (vinyl alcohol), poly (beta-hydroxybutyrate), poly (hydroxyvalerate), poly (hydroxybutyrate-co-polyester) and poly (glycolic acid).
8. The method for preparing the green and safe biodegradable material according to any one of claims 1 to 7, comprising the following steps:
mixing the preparation raw materials of the green safe biodegradable material to obtain a mixed material;
and processing and forming the mixed material to obtain the green safe biodegradable material.
9. The method for preparing the green and safe biodegradable material according to any one of claims 1 to 7, comprising the following steps:
mixing part of biodegradable polyester with other preparation raw materials of the green safe biodegradable material to obtain a primary mixed material;
extruding and granulating the primary mixed material to obtain biodegradable polyester master batch;
and mixing the biodegradable polyester master batch with the rest biodegradable polyester, and molding to obtain the green safe biodegradable material.
10. The use of the green safe biodegradable material according to any one of claims 1 to 7 or the green safe biodegradable material prepared by the preparation method according to any one of claims 8 to 9 in packaging or agricultural plastics.
CN202310854171.XA 2023-07-13 2023-07-13 Green safe biodegradable material and preparation method and application thereof Pending CN116589836A (en)

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Cited By (1)

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CN117126517A (en) * 2023-08-24 2023-11-28 江门市新会区岭南茶业有限公司 Environment-controllable degradable mulching film and application thereof in weeding

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