CN111114077A - Full-biodegradable bubble film and preparation process thereof - Google Patents

Full-biodegradable bubble film and preparation process thereof Download PDF

Info

Publication number
CN111114077A
CN111114077A CN201911371303.3A CN201911371303A CN111114077A CN 111114077 A CN111114077 A CN 111114077A CN 201911371303 A CN201911371303 A CN 201911371303A CN 111114077 A CN111114077 A CN 111114077A
Authority
CN
China
Prior art keywords
parts
bubble
layer
acid
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201911371303.3A
Other languages
Chinese (zh)
Inventor
周锐
李双利
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201911371303.3A priority Critical patent/CN111114077A/en
Publication of CN111114077A publication Critical patent/CN111114077A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/02—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents specially adapted to protect contents from mechanical damage
    • B65D81/03—Wrappers or envelopes with shock-absorbing properties, e.g. bubble films
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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
    • B65D2581/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D2581/02—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents specially adapted to protect contents from mechanical damage
    • B65D2581/05—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents specially adapted to protect contents from mechanical damage maintaining contents at spaced relation from package walls, or from other contents
    • B65D2581/051—Details of packaging elements for maintaining contents at spaced relation from package walls, or from other contents
    • B65D2581/052—Materials
    • B65D2581/055—Plastic in general, e.g. foamed plastic, molded plastic, extruded plastic
    • 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
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • 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
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic 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
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The invention discloses a full-biodegradable bubble film and a preparation process thereof. The full-biodegradable bubble film comprises a surface layer, a bubble layer and an inner layer which are sequentially compounded; the surface layer, the air bubble layer and the inner layer comprise the following raw materials in parts by weight: 10-20 parts of polylactic acid, 70-80 parts of polybutylene adipate-terephthalate, 0.03-0.07 part of antioxidant, 2-3 parts of biocompatible agent, 3-5 parts of heat sealing auxiliary agent, 1-2 parts of toughening agent and 5-9 parts of inorganic filler; the heat-sealing auxiliary agent comprises the following components: nonylphenol polyoxyethylene ether, diacetyl epoxy glycerol vegetable oleate, acetyl tributyl citrate, 2, 2' - (1, 3-phenylene) -bisoxazoline and 2,2, 2-trifluoroethyl methacrylate. The full-biodegradable bubble film has the advantages of high degradation speed, excellent mechanical property, high heat-sealing strength, good heat-insulating property and buffering shock resistance, and sound insulation and noise reduction.

Description

Full-biodegradable bubble film and preparation process thereof
Technical Field
The invention relates to the technical field of bubble films, in particular to a full-biodegradable bubble film and a preparation process thereof.
Background
The bubble film is a product which takes high-pressure polyethylene as a main raw material, is added with auxiliary materials such as whitening agent, opening agent and the like, is extruded and formed into bubbles at a high temperature of about 230 ℃ by plastic suction, is a novel plastic packaging material with light texture, high transparency, no toxicity and no odor, can play a role in releasing moisture, buffering, preserving heat and the like for the product, is also called a bubble pad, and is widely used for anti-seismic buffering packaging of electronic appliances, instruments, glass ceramics, artworks, hardware machinery, furniture and other furniture.
In the prior art, a chinese patent application No. 201610202026.3 discloses a film material for an air bubble bag and a preparation process thereof, wherein the film material comprises the following components in parts by weight: 15-20 parts of low-density polyethylene, 4-6 parts of 2, 2-dimethylolpropionic acid, 20-25 parts of isocyanate, 9-11 parts of methyltrichlorosilane, 4-6 parts of dioctyl adipate, 3-6 parts of erucamide, 10-12 parts of silicon dioxide, 3-4 parts of diphenyldichlorosilane, 1-1.5 parts of polyethylene glycol oleate and 1.2-1.5 parts of dicumyl peroxide.
After the film material is made into the bubble bag, the tensile strength, the light transmittance and the deformation resistance temperature are higher, and the oxygen transmittance is low, but the low-density polyethylene is used as the main raw material, but the degradation capability is poor, the degradation time is long after the film material is used, the pollution generated during degradation is larger, and the problem of white pollution is easily caused.
Polylactic acid (PLA) belongs to the most important biodegradable environment-friendly high polymer material in aliphatic polyester, has excellent biodegradability, can be completely degraded into carbon dioxide and water under the action of bacteria, water and the like, is harmless to the environment, and can thoroughly solve the problems of white pollution and the like caused by plastic products; but because the heat-resistant temperature is too low (softening point is 55 ℃), the use and the development of the PLA film are limited, the prior preparation process of the PLA film mostly adopts a blow molding mode to form the film, the film forming process has the problems of uneven film forming thickness, low transparency, low tensile strength and the like,
in the prior art, a chinese patent application No. 201610949553.0 discloses a biodegradable bubble film and a preparation process thereof, and the biodegradable bubble film comprises the following components in parts by mass: 5-40 parts of polylactic acid; 60-95 parts of polybutylene adipate-terephthalate; 0.5-2.0 parts of plasticizer; 0.5-2.0 parts of compatilizer; 0.2-0.5 part of chain extender; 0.1-0.5 part of slipping agent.
The biodegradable bubble film takes the environment-friendly biodegradable material polylactic acid and the poly adipic acid-butylene terephthalate with good biodegradability as raw materials, the prepared bubble film has degradability and excellent mechanical property, but because the solubility and the melting temperature of the polylactic acid and the poly adipic acid-butylene terephthalate are different greatly, the molten material is easy to extrude during heat sealing, the heat sealing part is shrunk and wrinkled, and the heat sealing strength and the shock resistance are reduced.
Therefore, the development of a bubble film with high degradation speed, excellent mechanical properties and high heat-sealing strength is an urgent problem to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a full-biodegradable bubble film which has the advantages of high degradation speed, excellent mechanical property and high heat-seal strength.
The second purpose of the invention is to provide a preparation process of the full-biodegradable bubble film, which has the advantages of simple process and easy operation.
In order to achieve the first object, the invention provides the following technical scheme: a full-biodegradable bubble film comprises a surface layer, a bubble layer and an inner layer which are sequentially compounded;
the surface layer, the air bubble layer and the inner layer comprise the following raw materials in parts by weight: 10-20 parts of polylactic acid, 70-80 parts of polybutylene adipate-terephthalate, 0.03-0.07 part of antioxidant, 2-3 parts of biocompatible agent, 3-5 parts of heat sealing auxiliary agent, 1-2 parts of toughening agent and 5-9 parts of inorganic filler;
the heat-sealing auxiliary agent comprises the following components in parts by weight: 3.2-4.6 parts of nonylphenol polyoxyethylene ether, 1.5-3 parts of diacetyl epoxy vegetable oil acid glyceride, 1.5-3 parts of acetyl tributyl citrate, 1.2-1.8 parts of 2, 2' - (1, 3-phenylene) -bisoxazoline and 0.8-1.6 parts of 2,2, 2-trifluoroethyl methacrylate.
By adopting the technical scheme, because polylactic acid and poly adipic acid-butylene terephthalate are adopted as main raw materials of the full-biodegradable bubble film, the polylactic acid and the poly adipic acid-butylene terephthalate are both degradable materials, the prepared bubble film has better degradability and high degradation speed, the compatibility of the polylactic acid and the poly adipic acid-butylene terephthalate can be improved by using a biological compatilizer, the mechanical properties of the bubble film, such as toughness, tensile strength and the like, can be improved by using a flexibilizer, the heat-sealing auxiliary agent is prepared by using nonylphenol polyoxyethylene ether and the like, the compatibility of the polylactic acid and the poly adipic acid-butylene terephthalate can be improved by using nonylphenol polyoxyethylene ether and 2,2, 2-trifluoroethyl methacrylate as the compatilizer, the melting point of a molten blend can be reduced by using diacetyl epoxy vegetable oil glyceride and tributyl acetylcitrate, so that the polylactic acid and the poly adipic acid-butylene terephthalate are easier to fuse, the tensile strength, the elongation at break and the tearing strength of the blend are increased to obtain good toughening effect, 2, 2' - (1, 3-phenylene) -bisoxazoline can increase the tensile strength and the thermal stability of polylactic acid, and reduce the melt flow speed, the cooling crystallization temperature and the crystallinity of the polylactic acid, so that the glass transition temperatures of the polylactic acid and the polybutylene adipate-terephthalate are similar, and the polylactic acid and the polybutylene adipate-terephthalate have excellent compatibility, similar melting temperature and glass transition temperature when being extruded and melted, so that the polylactic acid and the polybutylene adipate-terephthalate have similar melting time when being heat-sealed, and the polybutylene adipate-terephthalate is prevented from being melted and not being melted when being heat-sealed, so that the polybutylene adipate-terephthalate melted material is extruded, the shrinkage and wrinkling of the heat-sealing part are caused, so that the heat-sealing strength and the shock resistance of the heat-sealing part are improved, the diacetyl epoxy vegetable oil glyceride and the acetyl tributyl citrate are environment-friendly, and the biodegradation speed of the bubble film is not influenced.
Further, the surface layer, the air bubble layer and the inner layer are prepared from the following raw materials in parts by weight: 15 parts of polylactic acid, 75 parts of poly (butylene adipate-terephthalate), 0.05 part of antioxidant, 2.5 parts of biocompatible agent, 4 parts of heat-sealing auxiliary agent, 1.5 parts of toughening agent and 7 parts of inorganic filler;
the heat-sealing auxiliary agent comprises the following components in parts by weight: 3.9 parts of nonylphenol polyoxyethylene ether, 2 parts of diacetyl epoxy vegetable oil acid glyceride, 2 parts of acetyl tributyl citrate, 1.5 parts of 2, 2' - (1, 3-phenylene) -bisoxazoline and 1.2 parts of 2,2, 2-trifluoroethyl methacrylate.
Through adopting above-mentioned technical scheme, because the raw materials quantity of top layer, bubble layer and inlayer is more accurate for the bubble membrane mechanical properties who makes is excellent, has better shock resistance, puncture resistance and tensile strength, and heat-seal strength is high, is difficult for tearing.
Further, the polylactic acid is prepared by the following method:
(1) mixing lactic acid with stannous chloride and p-toluenesulfonic acid at the temperature of 100-120 ℃ under a vacuum condition, heating to the temperature of 145-160 ℃ for reaction for 1-2h, adding pentaerythritol, heating to the temperature of 170-180 ℃ for reaction for 1-2h, wherein the mass ratio of polylactic acid to stannous chloride to p-toluenesulfonic acid is 1 (0.005-0.01) to (0.005-0.01), and the mass ratio of lactic acid to pentaerythritol is 1: 0.4-0.5;
(2) adding toluene into the product obtained in the step (1), heating to 90-100 ℃, adding acrylic acid, p-toluenesulfonic acid and hydroquinone, heating to 120-150 ℃, reacting for 3-5h, vacuumizing, washing with acetone to obtain a semi-finished product of polylactic acid, wherein the mass ratio of lactic acid to toluene is 1:2.5-3, the mass ratio of lactic acid to p-toluenesulfonic acid to hydroquinone is 3 (0.01-0.03) to (0.003-0.005), and the mass ratio of acrylic acid to pentaerythritol is 3-5: 1;
(3) mixing 2.3-4.5 parts of stearic acid, 1.2-2.4 parts of titanate coupling agent and 8-12 parts of water by weight to prepare a mixed solution, putting 4.6-5.8 parts of nano calcium carbonate and 3.8-4.6 parts of nano silicon dioxide into the mixed solution, stirring for 3-5h, drying 10-15 parts of semi-finished polylactic acid at 70-80 ℃ for 6-8h, putting into 10-15 parts of polyethylene glycol with the mass concentration of 5%, adding pretreated nano calcium carbonate and nano silicon dioxide, mixing, extruding and granulating.
By adopting the technical scheme, pentaerythritol, acrylic acid and lactic acid are used to synthesize the double-bond-terminated polylactic acid with a branched structure, the glass transition temperature and the melting temperature of the polylactic acid are reduced due to the addition of the pentaerythritol, so that the polylactic acid and the poly adipic acid-dibutyl terephthalate have similar melting points, and the polylactic acid and the nano calcium carbonate and the nano silicon dioxide which are soaked by stearic acid and titanate coupling agent can play a role of a crystallization nucleating agent, the crystallization time of the polylactic acid is shortened, the crystallization temperature is reduced, the barrier capacity of the polylactic acid to water vapor can be increased due to the nano calcium carbonate and the nano silicon dioxide which are treated by the stearic acid and the titanate coupling agent, the moisture permeability coefficient of the polylactic acid is reduced, and the barrier property of the air bubble film is improved; mixing polylactic acid and polyethylene glycol can promote the hydrolysis reaction of polylactic acid and water, is favorable for water molecules to permeate into the polymer for hydrolysis, has good affinity with organisms, and can improve the degradation speed of polylactic acid.
Further, the inorganic filler is calcium carbonate, talcum powder and glass powder with the mass ratio of 5:1.7-2.3: 1.3-1.8.
By adopting the technical scheme, the calcium carbonate, the talcum powder and the glass powder are used as inorganic fillers, so that the tensile strength and the bending strength of the bubble film can be improved, the heat conductivity coefficient of the glass powder is small, the heat conductivity of the bubble film can be reduced, and the heat insulation effect of the bubble film is improved.
Further, the antioxidant comprises 2,2, 4-trimethyl-1, 2-dihydroquinoline, alkylaryl phosphite and nonylphenol polyoxyethylene ether phosphate, and the mass ratio of the 2,2, 4-trimethyl-1, 2-dihydroquinoline, the alkylaryl phosphite and the nonylphenol polyoxyethylene ether phosphate is 1:1.3-1.6: 0.8-1.2.
By adopting the technical scheme, the nonylphenol polyoxyethylene ether phosphate ester has strong antistatic property, smoothness and softness, and the alkylaryl phosphite ester can be matched with the 2,2, 4-trimethyl-1, 2-dihydroquinoline, so that the degradation speed of the bubble film is not influenced, and the mechanical property, the surface smoothness and the antistatic effect of the bubble film can be improved.
Furthermore, the thickness of the air bubble layer is 0.02-0.06mm, and the thickness of the surface layer and the inner layer is 0.015-0.035 mm; the bubble diameter of the bubbles in the bubble film is 8-12mm, and the bubble height is 3-5 mm.
Through adopting above-mentioned technical scheme, because the wearability of bubble mill is poor, place the easy gas leakage after the longer time, make its shock attenuation shock-absorbing capacity variation, influence the packaging quality of bubble bag, make the thickness on bubble layer great in the bubble membrane, bubble diameter and bubble height suit to the wearability of increase bubble membrane prevents that the bubble from leaking gas, thereby promotes the buffering shock attenuation performance of bubble membrane.
Further, the raw materials of the surface layer, the bubble layer and the inner layer also comprise the following components in parts by weight: 3.2-4.5 parts of degradable polyurethane, 1.4-2 parts of expanded starch and 1.2-2.4 parts of straw plant fiber.
By adopting the technical scheme, the degradable polyurethane, the puffed starch and the straw plant fiber are all degradable materials, the degradation speed of the air bubble film can be accelerated, the air bubble film can be fully degraded, no harmful substances are generated, the damping effect of the degradable polyurethane is good, the damping and noise reduction effects can be realized, the heat conductivity coefficient is small, the heat insulation effect is good, and the natural plant fiber and the puffed starch can enhance the sound insulation, damping, noise reduction, heat insulation, impact resistance and mechanical properties of the degradable polyurethane resin.
Further, the degradable polyurethane is prepared by the following method: drying 3-5 parts of bark of black wattle at 110 ℃ for 22-24h, crushing, adding into 6-10 parts of polyether polyol, stirring uniformly at high speed, sealing, standing at room temperature for 1-2d, adding 0.5-1 part of dibutyl tin dilaurate and 1-1.5 parts of silicone oil, mixing uniformly, adding 0.5-1 part of diphenylmethane diisocyanate under stirring at high speed, stirring for 1-2h, pouring into a mold preheated at 60-70 ℃ for 10-15min, standing at room temperature for 1-2h, taking out the mold, curing at room temperature for 7-10d, and crushing to obtain the particle size of 5-10 um.
By adopting the technical scheme, the bark containing tannin, polyether glycol and diphenylmethane diisocyanate are used for preparing the polyurethane, so that the bark containing tannin has better biodegradability and smaller heat conductivity coefficient, and the bark containing cellulose, lignin and other main components are macromolecules containing polyhydroxy radical, so that the bark can play a role of a cross-linking point, the toughness and the strength of the polyurethane are improved compared with those of the common polyurethane, and the bark containing tannin, polyether glycol and diphenylmethane diisocyanate has better sound absorption, sound insulation and buffering properties.
In order to achieve the second object, the invention provides the following technical scheme: a preparation process of a full-biodegradable bubble film comprises the following steps:
s1, preparing the surface layer, the bubble layer and the inner layer into granules according to the following method: drying polylactic acid and poly (butylene adipate-terephthalate) at 60-90 ℃ for 2-8h, adding a biological compatilizer, a flexibilizer, a heat-sealing auxiliary agent, an inorganic filler, an antioxidant, degradable polyurethane, expanded starch and straw plant fibers, uniformly mixing, adding into a double-screw extruder, and extruding and granulating to obtain granules;
s2, adding the inner layer granules and the bubble layer granules into a casting machine, extruding and casting to prepare an inner layer diaphragm and a bubble layer diaphragm, forming bubbles on the bubble layer diaphragm through a plastic suction bubble roller with the vacuum degree of 0.04-0.06MPa, and compounding the bubbles and the inner layer diaphragm through a compounding roller;
s3, extruding and casting the surface layer granules to form a surface layer membrane, and compounding the surface layer membrane with one side of the bubble layer with convex bubbles through a compounding roller to prepare the full-biodegradable bubble film.
By adopting the technical scheme, the raw materials of the inner layer and the bubble layer are simultaneously extruded and cast, the inner layer is compounded on the bubble layer formed by plastic suction, and the surface layer is compounded with the bubble layer after being extruded and cast, and the raw materials of the inner layer, the inner layer and the bubble layer are the same and have better biodegradation rate, excellent mechanical property and stronger heat sealing strength.
Further, in the step S1, the feeding section temperature of the twin-screw extruder is: 130 ℃ and 150 ℃, and the temperature of the plasticizing section: 170 ℃ and 190 ℃, and the temperature of the homogenization section: at the temperature of 200-; in the step S2, the extrusion temperature of the inner layer granules and the bubble layer granules is 200-250 ℃, and the composite pressure of the inner layer membrane and the bubble layer is 45-50kg/m2The compounding temperature is 55-80 ℃; the extrusion temperature of the surface layer granules in the step S3 is 170-190 ℃, and the composite pressure of the surface layer membrane and the bubble layer is 10-15kg/m2The compounding temperature is 50-70 ℃.
In conclusion, the invention has the following beneficial effects:
firstly, because the invention adopts polylactic acid and poly adipic acid-dibutyl terephthalate as the main raw materials of the inner surface layer, the air bubble layer and the inner layer of the air bubble film, and uses nonyl phenol polyoxyethylene ether, acetyl tributyl citrate and other substances to prepare the heat-sealing auxiliary agent, the compatibility of the polylactic acid and the poly adipic acid-dibutyl terephthalate can be increased by the acetyl tributyl citrate and the diacetyl epoxy vegetable oil glyceride, so that the polylactic acid and the poly adipic acid-dibutyl terephthalate are uniformly fused during heat sealing, the extrusion of the molten material is prevented, the wrinkling of the heat-sealing part is caused, and the impact strength is reduced.
Secondly, pentaerythritol and acrylic acid are preferably adopted to prepare the semi-finished polylactic acid, the glass transition temperature and the melting temperature of the polylactic acid are reduced due to the addition of the pentaerythritol, so that the polylactic acid has a melting temperature close to that of the poly-dibutyl adipate-terephthalate, and the poly-dibutyl adipate-terephthalate is prevented from being melted and extruded in advance during melting and heat sealing to cause wrinkling of a heat sealing part and reduce the impact resistance.
Thirdly, in the invention, the semi-finished polylactic acid is preferably dissolved in polyethylene glycol, and then mixed with nano calcium carbonate and nano silicon dioxide which are pretreated by stearic acid and titanate coupling agent to be extruded, the crystallization temperature of the polylactic acid is reduced by adding the nano calcium carbonate and the nano silicon dioxide, the crystallization time of the polylactic acid is shortened, the moisture permeability coefficient of the polylactic acid is reduced, the barrier property of a bubble film is increased, the hydrophilicity of the polylactic acid is increased by adding the polyethylene glycol, and the degradation speed of the polylactic acid is increased.
Fourthly, in the invention, preferably, degradable polyurethane, expanded starch and straw plant fiber are added into the surface layer, the air bubble layer and the inner layer, and bark and polyether polyol are used for preparing the degradable polyurethane so as to increase the degradation speed of the air bubble film and the noise reduction, heat preservation and buffer performance, and the straw plant fiber and the expanded starch can increase the sound insulation, shock absorption, heat preservation, impact resistance and other performances of the degradable polyurethane.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation examples 1 to 3 of polylactic acid
The titanate coupling agent in preparation examples 1 to 3 is selected from the titanate coupling agent sold by green Wei plastic products, Inc. of Dongguan city and having the model number NDZ-201, the nano calcium carbonate is selected from the nano calcium carbonate sold by Baifeng mineral processing factories of Ling county and having the product number 14, and the nano silica is selected from the nano silica sold by Aidehan chemical industries, Inc. of Quzhou city and having the model number A200.
Preparation example 1: (1) rotationally evaporating 88 mass percent of lactic acid aqueous solution at 65 ℃ under the absolute pressure of 1000Pa for 2h, then mixing with stannous chloride and p-toluenesulfonic acid at 100 ℃ under the vacuum condition, heating to 145 ℃ for reacting for 2h, adding pentaerythritol, heating to 170 ℃ for reacting for 2h, wherein the mass ratio of polylactic acid, stannous chloride and p-toluenesulfonic acid is 1:0.005:0.005, and the mass ratio of lactic acid to pentaerythritol is 1: 0.4;
(2) adding toluene into the product obtained in the step (1), heating to 90 ℃, adding acrylic acid, p-toluenesulfonic acid and hydroquinone, heating to 120 ℃, reacting for 5 hours, vacuumizing, washing with acetone to obtain a semi-finished product of polylactic acid, wherein the mass ratio of lactic acid to toluene is 1:2.5, the mass ratio of lactic acid to p-toluenesulfonic acid to hydroquinone is 3:0.01:0.003, and the mass ratio of acrylic acid to pentaerythritol is 3: 1;
(3) mixing 2.3kg of stearic acid, 1.2kg of titanate coupling agent and 8kg of water to prepare a mixed solution, placing 4.6kg of nano calcium carbonate and 3.8kg of nano silicon dioxide in the mixed solution, stirring for 3h, drying 10kg of semi-finished polylactic acid at 70 ℃ for 8h, placing in 10kg of polyethylene glycol with the mass concentration of 5%, adding the pretreated nano calcium carbonate and nano silicon dioxide, mixing, extruding at 200 ℃ and granulating.
Preparation example 2: (1) rotationally evaporating 88% by mass of lactic acid aqueous solution at 65 ℃ under the absolute pressure of 1000Pa for 2h, then mixing with stannous chloride and p-toluenesulfonic acid at 110 ℃ under the vacuum condition, heating to 150 ℃ for reaction for 1.5h, adding pentaerythritol, heating to 175 ℃ for reaction for 1.5h, wherein the mass ratio of polylactic acid to stannous chloride to p-toluenesulfonic acid is 1:0.008:0.008, and the mass ratio of lactic acid to pentaerythritol is 1: 0.45;
(2) adding toluene into the product obtained in the step (1), heating to 95 ℃, adding acrylic acid, p-toluenesulfonic acid and hydroquinone, heating to 135 ℃, reacting for 4 hours, vacuumizing, washing with acetone to obtain a semi-finished product of polylactic acid, wherein the mass ratio of lactic acid to toluene is 1:2.8, the mass ratio of lactic acid to p-toluenesulfonic acid to hydroquinone is 3:0.02:0.004, and the mass ratio of acrylic acid to pentaerythritol is 4: 1;
(3) mixing 3.4kg of stearic acid, 1.8kg of titanate coupling agent and 10kg of water to prepare a mixed solution, placing 5.2kg of nano calcium carbonate and 4.2kg of nano silicon dioxide in the mixed solution, stirring for 4h, drying 13kg of semi-finished polylactic acid at 75 ℃ for 7h, placing in 13kg of polyethylene glycol with the mass concentration of 5%, adding the pretreated nano calcium carbonate and nano silicon dioxide, mixing, extruding at 205 ℃, and granulating.
Preparation example 3: (1) rotationally evaporating 88 mass percent of lactic acid aqueous solution at 65 ℃ under the absolute pressure of 1000Pa for 2 hours, then mixing with stannous chloride and p-toluenesulfonic acid at 120 ℃ under the vacuum condition, heating to 160 ℃ for reaction for 1 hour, adding pentaerythritol, heating to 180 ℃ for reaction for 1 hour, wherein the mass ratio of polylactic acid to stannous chloride to p-toluenesulfonic acid is 1:0.01:0.01, and the mass ratio of lactic acid to pentaerythritol is 1: 0.5;
(2) adding toluene into the product obtained in the step (1), heating to 100 ℃, adding acrylic acid, p-toluenesulfonic acid and hydroquinone, heating to 150 ℃, reacting for 3 hours, vacuumizing, washing with acetone to obtain a semi-finished product of polylactic acid, wherein the mass ratio of lactic acid to toluene is 1:3, the mass ratio of lactic acid to p-toluenesulfonic acid to hydroquinone is 3:0.03:0.005, and the mass ratio of acrylic acid to pentaerythritol is 5: 1;
(3) mixing 4.5kg of stearic acid, 2.4kg of titanate coupling agent and 12kg of water to prepare a mixed solution, placing 5.8kg of nano calcium carbonate and 4.6kg of nano silicon dioxide in the mixed solution, stirring for 5h, drying 15kg of semi-finished polylactic acid at 80 ℃ for 6h, placing in 15kg of polyethylene glycol with the mass concentration of 5%, adding the pretreated nano calcium carbonate and nano silicon dioxide, mixing, extruding at 210 ℃ and granulating.
Preparation examples 4 to 6 of degradable polyurethanes
Preparation examples 4 to 6 the polyether polyol was selected from the polyether polyol sold by Haian petrochemical plant of Jiangsu province under the model number P-123, the dibutyltin dilaurate was selected from Wajie specialization technology, Inc. of Nanjing, and the silicone oil was selected from the silicone oil sold by Jiashan Jiangnan textile materials, Inc. under the model number JF-201.
Preparation example 4: drying 3kg of acacia negra bark at 105 ℃ for 24h, crushing, adding into 6kg of polyether polyol, stirring uniformly at a high speed, sealing, standing at room temperature for 1d, adding 0.5kg of dibutyl tin dilaurate and 1kg of silicone oil, mixing uniformly, adding 0.5kg of diphenylmethane diisocyanate under stirring at a high speed, stirring for 1h, pouring into a mold preheated at 60 ℃ for 15min, standing at room temperature for 1h, taking out the mold, curing at room temperature for 7d, and crushing to obtain the particle size of 5 microns.
Preparation example 5: drying 4kg of acacia negra bark at 108 ℃ for 23h, crushing, adding into 8kg of polyether polyol, stirring uniformly at high speed, sealing, standing at room temperature for 2d, adding 0.8kg of dibutyltin dilaurate and 1.3kg of silicone oil, mixing uniformly, adding 0.8kg of diphenylmethane diisocyanate under high speed stirring, stirring continuously for 1.5h, pouring into a mold preheated at 65 ℃ for 13min, standing at room temperature for 1.5h, taking the mold down, curing at room temperature for 8d, and crushing to obtain the particle size of 8 mu m.
Preparation example 6: drying 5kg of acacia negra bark at 110 ℃ for 22h, crushing, adding into 10kg of polyether polyol, stirring uniformly at high speed, sealing, standing at room temperature for 2d, adding 1kg of dibutyl tin dilaurate and 1.5kg of silicone oil, mixing uniformly, adding 1kg of diphenylmethane diisocyanate under high speed stirring, stirring continuously for 2h, pouring into a mold preheated at 70 ℃ for 10min, standing at room temperature for 2h, taking out the mold, curing at room temperature for 10d, and crushing to obtain the particle size of 10 microns.
Examples
In the following examples, the tributyl acetylcitrate is selected from FF454 tributyl acetylcitrate sold by Wuhananapoli pharmaceutical chemical Co., Ltd, the diacetyl epoxy glyceryl oleate is selected from nonylphenol polyoxyethylene ether sold by Hai code group with HM-828, the nonylphenol polyoxyethylene ether is selected from nonylphenol polyoxyethylene ether sold by Guangzhou Jia Cheng chemical Co., Ltd with NP15, the 2,2 '- (1, 3-phenylene) -bisoxazoline is selected from 2, 2' - (1, 3-phenylene) -bisoxazoline sold by Jining HuaKai resin Co., Ltd with 34052-90-9, the 2,2, 2-trifluoroethyl methacrylate is selected from Weihai Xinyuan chemical Co., Ltd, the toughening agent is selected from a toughening agent sold by Wake chemical Co., Ltd with VINNEX 2505, the biological compatilizer is selected from a good easy compatilizer SOG-008 model biocompatible sold by Jiangsu Limited, the alkylaryl phosphite is selected from DPDPDTNPP model alkylaryl phosphite sold by Shanghai Guangbin trade Limited, the nonylphenol polyoxyethylene ether phosphate is selected from NP-10P model nonylphenol polyoxyethylene ether phosphate sold by Wuhan Dahua Wei pharmaceutical chemical Limited, the puffed starch is selected from 009 puffed starch sold by Henan Suda starch adhesive Limited, and the straw plant fiber is selected from ECP model straw plant fiber sold by Hangzhou Gaokou composite material Limited.
Example 1: the utility model provides a full biodegradable bubble membrane, is including compound top layer, bubble layer and inlayer in proper order, and the thickness on top layer and inlayer is 0.015mm, and the thickness on bubble layer is 0.02mm, and the bubble footpath of bubble in the bubble layer is 8mm, and the bubble height is 3mm, and the raw materials and the quantity on top layer, bubble layer and inlayer are the same, as shown in Table 1, this preparation technology of full biodegradable bubble membrane includes following steps:
s1, preparing the surface layer, the bubble layer and the inner layer into granules according to the following method: drying 10kg of polylactic acid and 80kg of poly (butylene adipate-terephthalate) at 60 ℃ for 8h, adding 2kg of a biocompatible agent, 1kg of a toughening agent, 3kg of a heat-sealing auxiliary agent, 5kg of an inorganic filler and 0.03kg of an antioxidant, uniformly mixing, adding into a double-screw extruder, and extruding and granulating to obtain granules, wherein the temperature of a feeding section of the double-screw extruder is 130 ℃, the temperature of a plasticizing section is 170 ℃, the temperature of a homogenizing section is 200 ℃, the rotating speed of a screw is 150r/min, and the length-diameter ratio of the screw is 32: 1;
wherein polylactic acid is prepared from preparation example 1, the weight average molecular weight of polybutylene terephthalate-polyethylene glycol is 20000Da, and the heat sealing auxiliary agent is prepared from the raw materials in Table 2 according to the following method: heating 1.5kg of acetyl tributyl citrate and 1.5kg of diacetyl epoxy vegetable oil acid glyceride to 350 ℃, stirring at the speed of 1000r/min for 2h, adding 3.2kg of nonylphenol polyoxyethylene ether, continuing to stir for 20min, cooling to 210 ℃, adding 1.2kg of 2, 2' - (1, 3-phenylene) -bisoxazoline and 0.8kg of 2,2, 2-trifluoroethyl methacrylate, and stirring at the rotating speed of 500r/min for 30 min; the inorganic filler is prepared by mixing calcium carbonate, talcum powder and glass powder in a mass ratio of 5:1.7:1.3, wherein the particle size of the calcium carbonate is 5 mu m, the particle size of the talcum powder is 0.5 mu m, the particle size of the glass powder is 0.3 mu m, and the antioxidant is 2,2, 4-trimethyl-1, 2-dihydroquinoline, alkylaryl phosphite ester and nonylphenol polyoxyethylene ether phosphate in a mass ratio of 1:1.3: 0.8;
s2, adding the inner layer granules and the bubble layer granules into a casting machine, extruding and casting to prepare an inner layer diaphragm and a bubble layer diaphragm, forming bubbles on the bubble layer diaphragm through a plastic suction bubble roller with the vacuum degree of 0.04MPa, and compounding the bubble layer diaphragm and the inner layer diaphragm through a compounding roller, wherein the extrusion temperature of the inner layer granules and the bubble layer granules is 200 ℃, and the compounding pressure of the inner layer diaphragm and the bubble layer is 45kg/cm2The compounding temperature is 80 ℃;
s3, extruding and casting the surface layer granules to form a surface layer membrane, and compounding the surface layer membrane with one side of the bubble layer with convex bubbles through a compounding roller to prepare the fully biodegradable bubble film, wherein the extrusion temperature of the surface layer granules is 170 ℃, and the compounding pressure of the surface layer membrane and the bubble layer is 10kg/cm2The compounding temperature is 50 ℃.
TABLE 1 raw material ratios of the surface layer, the bubble layer and the inner layer in the fully biodegradable bubble film in examples 1 to 5
Figure BDA0002339713660000091
TABLE 2 raw material ratios of heat-seal auxiliary in examples 1 to 5
Figure BDA0002339713660000092
Figure BDA0002339713660000101
Example 2: the utility model provides a full biodegradable bubble membrane, is including compound top layer, bubble layer and inlayer in proper order, and the thickness on top layer and inlayer is 0.025mm, and the thickness on bubble layer is 0.04mm, and the bubble footpath of bubble in the bubble layer is 10mm, and the bubble height is 4mm, and the raw materials and the quantity on top layer, bubble layer and inlayer are the same, as shown in Table 1, this preparation technology of full biodegradable bubble membrane includes following steps:
s1, preparing the surface layer, the bubble layer and the inner layer into granules according to the following method: drying 13kg of polylactic acid and 77kg of poly (butylene adipate-terephthalate) at 75 ℃ for 5h, adding 2.3kg of a biological compatilizer, 1.3kg of a toughening agent, 3.5kg of a heat-sealing assistant, 6kg of an inorganic filler and 0.04kg of an antioxidant, uniformly mixing, adding the mixture into a double-screw extruder, extruding and granulating to obtain granules, wherein the temperature of a feeding section of the double-screw extruder is 140 ℃, the temperature of a plasticizing section is 180 ℃, the temperature of a homogenizing section is 210 ℃, the rotating speed of a screw is 250r/min, and the length-diameter ratio of the screw is 36: 1;
wherein polylactic acid is prepared from preparation example 2, the weight average molecular weight of the polybutylene terephthalate-polyethylene glycol is 70000Da, and the heat-sealing auxiliary agent is prepared from the raw materials in the following method in Table 2: heating 1.8kg of acetyl tributyl citrate and 1.8kg of diacetyl epoxy vegetable oil acid glyceride to 380 ℃, stirring at the speed of 1500r/min for 1.5h, adding 3.6kg of nonylphenol polyoxyethylene ether, continuing stirring for 30min, cooling to 210 ℃, adding 1.3kg of 2, 2' - (1, 3-phenylene) -bisoxazoline and 1.0kg of 2,2, 2-trifluoroethyl methacrylate, and stirring at the rotating speed of 800r/min for 20 min; the inorganic filler is prepared by mixing calcium carbonate, talcum powder and glass powder in a mass ratio of 5:2:1.4, wherein the particle size of the calcium carbonate is 8 mu m, the particle size of the talcum powder is 0.8 mu m, the particle size of the glass powder is 0.5 mu m, and the antioxidant is 2,2, 4-trimethyl-1, 2-dihydroquinoline, alkylaryl phosphite ester and nonylphenol polyoxyethylene ether phosphate in a mass ratio of 1:1.4: 1;
s2, adding the inner layer granules and the bubble layer granules into a casting machine, extruding and casting to prepare an inner layer diaphragm and a bubble layer diaphragm, forming bubbles on the bubble layer diaphragm through a plastic suction bubble roller with the vacuum degree of 0.05MPa, and compounding the bubble layer diaphragm and the inner layer diaphragm through a compounding roller, wherein the extrusion temperature of the inner layer granules and the bubble layer granules is 230 ℃, and the compounding pressure of the inner layer diaphragm and the bubble layer is 48kg/cm2The compounding temperature is 65 ℃;
s3, extruding and casting the surface layer granules to form a surface layer membrane, and compounding the surface layer membrane with one side of the bubble layer with convex bubbles through a compounding roller to prepare the fully biodegradable bubble film, wherein the extrusion temperature of the surface layer granules is 180 ℃, and the compounding pressure of the surface layer membrane and the bubble layer is 13kg/cm2The compounding temperature is 60 ℃.
Example 3: the utility model provides a full biodegradable bubble membrane, is including compound top layer, bubble layer and inlayer in proper order, and the thickness on top layer and inlayer is 0.035mm, and the thickness on bubble layer is 0.06mm, and the bubble footpath of bubble in the bubble layer is 12mm, and the bubble height is 5mm, and the raw materials and the quantity on top layer, bubble layer and inlayer are the same, as shown in Table 1, this preparation technology of full biodegradable bubble membrane includes following step:
s1, preparing the surface layer, the bubble layer and the inner layer into granules according to the following method: drying 15kg of polylactic acid and 75kg of poly (butylene adipate-terephthalate) at 90 ℃ for 2h, adding 2.5kg of a biological compatilizer, 1.5kg of a toughening agent, 4kg of a heat sealing assistant, 7kg of an inorganic filler and 0.05kg of an antioxidant, uniformly mixing, adding into a double-screw extruder, extruding and granulating to obtain granules, wherein the temperature of a feeding section of the double-screw extruder is 150 ℃, the temperature of a plasticizing section is 190 ℃, the temperature of a homogenizing section is 220 ℃, the rotating speed of a screw is 350r/min, and the length-diameter ratio of the screw is 40: 1;
wherein polylactic acid was prepared from preparation example 3, the weight average molecular weight of polybutylene terephthalate-polyethylene glycol was 120000Da, and the heat-seal auxiliary was prepared from the raw materials in Table 2 by the following method: heating 2kg of acetyl tributyl citrate and 2kg of diacetyl epoxy vegetable oil acid glyceride to 400 ℃, stirring at the speed of 2000r/min for 1h, adding 3.9kg of nonylphenol polyoxyethylene ether, continuing to stir for 40min, cooling to 215 ℃, adding 1.5kg of 2, 2' - (1, 3-phenylene) -bisoxazoline and 1.2kg of 2,2, 2-trifluoroethyl methacrylate, and stirring at the rotating speed of 1000r/min for 10 min; the inorganic filler is prepared by mixing calcium carbonate, talcum powder and glass powder in a mass ratio of 5:2.3:1.8, wherein the particle size of the calcium carbonate is 10 mu m, the particle size of the talcum powder is 1 mu m, the particle size of the glass powder is 0.8 mu m, and the antioxidant is 2,2, 4-trimethyl-1, 2-dihydroquinoline, alkylaryl phosphite ester and nonylphenol polyoxyethylene ether phosphate in a mass ratio of 1:1.6: 1.2;
s2, adding the inner layer granules and the bubble layer granules into a casting machine, extruding and casting to prepare an inner layer diaphragm and a bubble layer diaphragm, forming bubbles on the bubble layer diaphragm through a plastic suction bubble roller with the vacuum degree of 0.06MPa, and compounding the bubble layer diaphragm and the inner layer diaphragm through a compounding roller, wherein the extrusion temperature of the inner layer granules and the bubble layer granules is 250 ℃, and the compounding pressure of the inner layer diaphragm and the bubble layer is 50kg/cm2The compounding temperature is 55 ℃;
s3, extruding and casting the surface layer granules to form a surface layer membrane,then compounding the surface layer diaphragm with one side of the bubble layer with convex bubbles through a compounding roller to prepare the fully biodegradable bubble film, wherein the extrusion temperature of the surface layer granules is 190 ℃, and the compounding pressure of the surface layer diaphragm and the bubble layer is 15kg/cm2The compounding temperature is 70 ℃.
Examples 4 to 5: a fully biodegradable bubble film was prepared as described in example 1, except that the formulation of the raw materials for the surface layer, the bubble layer and the inner layer, in which polylactic acid was prepared as described in preparation example 1, and the formulation of the raw material for the heat-sealing aid was as described in Table 2.
Example 6: a fully biodegradable bubble film, which is different from example 1 in that, when pellets are prepared in step S1, the surface layer, the bubble layer and the inner layer further include 3.2kg of degradable polyurethane, 1.4kg of expanded starch and 1.2kg of straw plant fiber, and the degradable polyurethane is prepared in preparation example 4.
Example 7: a fully biodegradable bubble film, which is different from example 1 in that, when pellets are prepared in step S1, the surface layer, the bubble layer and the inner layer further include 3.8kg of degradable polyurethane, 1.7kg of expanded starch and 1.8kg of straw plant fiber, and the degradable polyurethane is prepared in preparation example 5.
Example 8: a fully biodegradable bubble film, which is different from example 1 in that, when pellets are prepared in step S1, the surface layer, the bubble layer and the inner layer further include 4.5kg of degradable polyurethane, 2kg of expanded starch and 2.4kg of straw plant fiber, the degradable polyurethane being prepared in preparation example 6.
Comparative example
Comparative example 1: a fully biodegradable bubble film was prepared in a manner different from that of example 1 in that polylactic acid was used in an amount of 5kg and polybutylene adipate-terephthalate was used in an amount of 85kg in the surface layer, the bubble layer and the inner layer.
Comparative example 2: a fully biodegradable bubble film was prepared in a manner different from that of example 1 in that polylactic acid was used in an amount of 25kg and polybutylene adipate-terephthalate was used in an amount of 65kg in the surface layer, the bubble layer and the inner layer.
Comparative example 3: a full-biodegradable bubble film is different from that in example 1 in that nonylphenol polyoxyethylene ether and 2,2, 2-trifluoroethyl methacrylate are not added in heat sealing aids in a surface layer, a bubble layer and an inner layer.
Comparative example 4: a fully biodegradable bubble film is different from that in example 1 in that diacetyl epoxy vegetable olein and acetyl tributyl citrate are not added in the heat sealing auxiliary agents in the surface layer, the bubble layer and the inner layer.
Comparative example 5: a fully biodegradable bubble film, which differs from example 1 in that polylactic acid is replaced with 3001D, a polylactic acid sold by suzhou nfu plastics ltd.
Comparative example 6: a fully biodegradable air bubble film was obtained, which was different from example 1 in that the antioxidant was replaced with an antioxidant 1010 sold by Shanghai Tianchang trade Co., Ltd.
Comparative example 7: a fully biodegradable bubble film was prepared, which was different from example 1 in that no glass frit was added to the inorganic filler.
Comparative example 8: a fully biodegradable bubble film, differing from example 6 in that the degradable polyurethane was replaced with 1170A marketed by suzhou strong plasticization limited.
Comparative example 9: a fully biodegradable bubble film is different from the bubble film in example 6 in that straw plant fiber and expanded starch are not added.
Comparative example 10: the biodegradable bubble film prepared in example 1 of the chinese invention patent with application number 201610949553.0 was used as a control, and included the following components: 40 parts of polylactic acid, 60 parts of poly adipic acid-butylene terephthalate, 2 parts of acetyl citrate triester, 20002 parts of polyethylene glycol, 0.2 part of ethylene-methyl acrylate-glycidyl methacrylate terpolymer and 0.5 part of oleamide.
Performance test
Firstly, mechanical property detection: bubble films were prepared according to the methods of examples 1 to 8 and comparative examples 1 to 10, and the films were pressed at a pressure of 0.3MPa and a temperature of 130 ℃ for 2 seconds to prepare film samples of 64cm × 100cm, and the mechanical properties of the bubble films were measured according to the following methods, and the measurement results are recorded in table 3:
1. tensile strength and tensile modulus: testing according to GB13022-1991 method for testing tensile property of plastic films;
2. elongation at break: determination of tensile Properties of plastics according to GB/T1040.3-2006 part 3: test conditions for films and sheets ";
3. dart impact mass: testing according to GB/T9639-1988, the free dart method of the test method of the impact resistance of the plastic film and the sheet;
4. puncture strength: testing according to GB/T10004 'method for testing puncture strength of packaging plastic composite films';
5. heat seal strength: the test is carried out according to GB/T2358-1998 test method for heat seal strength of plastic film packaging bags.
TABLE 3 measurement of mechanical Properties of bubble films prepared in examples 1 to 8 and comparative examples 1 to 10
Figure BDA0002339713660000131
As can be seen from the data in Table 3, the bubble films prepared according to the methods of examples 1 to 5 have high longitudinal tensile strength, transverse tensile strength, longitudinal tensile modulus and transverse tensile modulus, high elongation at break, high drop weight impact mass and high puncture resistance, and the heat seal strength reaches (13.8 to 15.3) N/15mm, which shows that the bubble films prepared according to examples 1 to 6 of the present invention have good heat sealability, high tensile strength, high tensile modulus, high elongation at break, high puncture resistance, impact resistance and high mechanical strength after being made into packaging bags.
Examples 6 to 8, in which degradable polyurethane, expanded starch and straw plant fiber were blended, all of the tensile strength, elongation at break, heat seal strength, puncture strength and drop hammer impact quality of the resulting bubble films were enhanced, which indicates that the incorporation of degradable polyurethane, expanded starch and straw plant fiber can enhance the properties of the bubble films, such as impact strength, tensile strength, elongation at break and heat seal strength.
In comparative example 1, the use amount of polylactic acid is 5kg, the use amount of polybutylene adipate-terephthalate is 85kg, the use amount of polylactic acid is reduced, the use amount of polybutylene adipate-terephthalate is increased, in comparative example 2, the use amount of polybutylene adipate-terephthalate is reduced, the transverse tensile strength and the longitudinal tensile strength of the bubble films prepared in comparative examples 1 and 2 are reduced, the puncture resistance strength and the drop weight impact quality are reduced, and the heat sealing strength is reduced, so that 10-20 parts of polylactic acid and 70-80 parts of polybutylene adipate-terephthalate are used, and the bubble films with excellent mechanical properties and good heat sealing properties can be prepared.
In comparative example 3, because nonylphenol polyoxyethylene ether and 2,2, 2-trifluoroethyl methacrylate are not added to the heat-seal auxiliary agent, and after polylactic acid and polybutylene adipate-terephthalate are blended, the compatibility and the dispersibility are reduced, so that the properties of the prepared bubble film, such as tensile strength, puncture resistance and the like, are reduced, the heat-seal strength is reduced, and the heat-seal property is poor.
Comparative example 4 since diacetyl epoxy vegetable olein and acetyl tributyl citrate were not added to the heat-sealing aid, the properties of the bubble film prepared in comparative example 4 were all reduced compared to example 1.
Comparative example 5 a bubble film prepared by using a commercially available polylactic acid instead of the polylactic acid used in the present invention was degraded in mechanical properties, and both the puncture resistance effect and the heat-seal strength were reduced.
In comparative example 6, a commercial 1010 antioxidant was used instead of the antioxidant used in the present invention, and it is found from the results of the test that the properties of the bubble film prepared in comparative example 6 are not much different from those of example 1, but are still reduced.
In comparative example 7, since glass powder was not added to the inorganic filler, the tensile strength of the bubble film was reduced, the elongation at break was reduced, and the impact strength was deteriorated.
Comparative example 8 in which commercially available polyurethane was used instead of the degradable polyurethane prepared according to the present invention, and comparative example 9 in which straw plant fiber and expanded starch were not added, it was found from the results of the test that the bubble films prepared according to comparative examples 8 and 9 had lower tensile strength, lower elongation at break, lower mechanical properties than those of the bubble films prepared according to examples 6 to 8, lower heat seal strength, and lower heat seal properties than those of the bubble films prepared according to examples 6 to 8.
Comparative example 10 is a bubble film prepared by the prior art, which has poor tensile strength and puncture resistance, although the elongation at break is high.
Secondly, detecting the biodegradation rate: bubble films were prepared according to the methods of examples 1 to 8 and comparative examples 1 to 10, 100 pieces of bubble films having a length of 150mm and a width of 15mm were taken for each example and each comparative example, and the bubble films were tested according to HJ/T209-2005 "environmental labeling product requirements packaging product", and the test results of 100 pieces of bubble films for each example or comparative example were averaged and recorded in Table 4.
TABLE 4 measurement of biodegradation rates of bubble films prepared in examples 1 to 8 and comparative examples 1 to 10
Figure BDA0002339713660000151
As can be seen from the data in Table 4, the bubble films prepared by the methods of examples 1 to 8 have a degradation rate of 98.5 to 100% in 110 days, and complete 100% degradation in 120 days, with a rapid degradation rate.
Comparative example 1 the biodegradation rate of the bubble films prepared in comparative examples 1 and 2 was not much different from examples 1 to 8 because the amount of polylactic acid used was 5kg and the amount of polybutylene adipate-terephthalate used was 85kg, the amount of polylactic acid used was decreased and the amount of polybutylene adipate-terephthalate used was increased, and comparative example 2 the amount of polybutylene adipate-terephthalate used was decreased because the amount of polylactic acid used was increased.
Comparative example 3 because nonylphenol polyoxyethylene ether and 2,2, 2-trifluoroethyl methacrylate were not added to the heat-seal auxiliary, and comparative example 4 because diacetyl epoxy vegetable olein and acetyl tributyl citrate were not added to the heat-seal auxiliary, it can be seen from the comparison of the results in table 3 that the degradation rates of the bubble films prepared in comparative example 3 and comparative example 4 are faster, and almost 100% full degradation is achieved in 120 days.
Comparative example 5 since the commercially available polylactic acid was used instead of the polylactic acid prepared according to the present invention, the degradation rate of the bubble film prepared according to comparative example 5 was relatively slow, only 91.2% in 120 days, and the degradation rate was inferior to that of examples 1 to 8 according to the present invention.
Comparative example 6 a commercially available 1010 type antioxidant was used instead of the antioxidant used in the present invention, and the degradation rate of the bubble film prepared in comparative example 6 was only 58.3% at 80 days and 94.3% at 120 days, which was not as fast as the degradation rates of the bubble films prepared in examples 1 to 8 of the present invention.
Comparative example 7 since glass powder was not added to the inorganic filler, the degradation rate of the bubble film gas prepared in comparative example 7 was not much different from that of example 1, and had a faster degradation rate.
Comparative example 8 since the degradable polyurethane prepared according to the present invention was replaced with the commercially available polyurethane, the degradation rate of the bubble film prepared according to comparative example 8 was 98.8% at 110 days and was still 96.8% at 120 days, and the degradation was not complete, whereas the bubble film prepared according to example 6 was completely degraded by 100% at 120 days, and thus the degradation rate of the bubble film was reduced using the commercially available degradable polyurethane.
In comparative example 9, since the straw plant fiber and the expanded starch were not added, the degradation rate of the bubble film was reduced and the degradation rate was slowed compared with example 6.
Comparative example 10 is a bubble film prepared in the prior art, which had a degradation rate of only 95.4 in 120 days, and the longer the degradation time, the slower the degradation rate, which was lower than that of the bubble films prepared in examples 1 to 8 of the present invention.
Thirdly, detecting the heat preservation and noise reduction performance: bubble films were prepared according to the methods of examples 6 to 8 and comparative examples 7 to 10, and the heat-retaining and noise-reducing properties of the bubble films were measured according to the following methods, and the measurement results are recorded in table 5:
1. coefficient of thermal conductivity: detecting according to GB/T3399-1982 protective hot plate method for plastic thermal conductivity coefficient test method;
2. sound insulation amount: the normal incidence acoustic transmission loss of the membrane was tested on the transmission matrix method with reference to the ASTM E2611-09 standard plane using a four channel impedance tube (model 4206T) from B & K.
TABLE 5 test for noise reduction and heat retention of bubble films prepared in examples 6 to 8 and comparative examples 7 to 10
Figure BDA0002339713660000161
Figure BDA0002339713660000171
As can be seen from the data in Table 5, the bubble films prepared in examples 6 to 8, which incorporate degradable polyurethane, expanded starch and straw plant fiber, have small thermal conductivity, large sound insulation, and good heat preservation and noise reduction effects.
Comparative example 7 since glass powder was not added to the inorganic filler, the bubble film prepared in comparative example 7 had a large difference in thermal conductivity from examples 6 to 8, but did not have a large difference in sound insulation for different frequencies of noise, indicating that the use of glass powder as a filler enhances the heat insulating properties of the bubble film.
Comparative example 8 since commercially available polyurethane was used instead of the degradable polyurethane used in the present invention, the thermal conductivity of the bubble film prepared in comparative example 8 was improved and the reduction in sound insulation was significant, indicating that the degradable polyurethane used in the present invention can improve the sound insulation effect of the bubble film and increase the heat insulation performance.
In the comparative example 9, the straw plant fiber and the expanded starch are not added, so that the bubble film prepared in the comparative example 9 is large in heat conductivity coefficient, small in sound insulation amount and reduced in heat preservation and noise reduction effects.
Comparative example 10 is a bubble film prepared in the prior art, which has a sound insulation effect and a heat preservation effect inferior to those of the bubble films prepared in examples 6 to 8 of the present invention.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (10)

1. A full-biodegradable bubble film is characterized by comprising a surface layer, a bubble layer and an inner layer which are sequentially compounded;
the surface layer, the air bubble layer and the inner layer comprise the following raw materials in parts by weight: 10-20 parts of polylactic acid, 70-80 parts of polybutylene adipate-terephthalate, 0.03-0.07 part of antioxidant, 2-3 parts of biocompatible agent, 3-5 parts of heat sealing auxiliary agent, 1-2 parts of toughening agent and 5-9 parts of inorganic filler;
the heat-sealing auxiliary agent comprises the following components in parts by weight: 3.2-4.6 parts of nonylphenol polyoxyethylene ether, 1.5-3 parts of diacetyl epoxy vegetable oil acid glyceride, 1.5-3 parts of acetyl tributyl citrate, 1.2-1.8 parts of 2, 2' - (1, 3-phenylene) -bisoxazoline and 0.8-1.6 parts of 2,2, 2-trifluoroethyl methacrylate.
2. The fully biodegradable bubble film according to claim 1, wherein the surface layer, the bubble layer and the inner layer are prepared from the following raw materials in parts by weight: 15 parts of polylactic acid, 75 parts of poly (butylene adipate-terephthalate), 0.05 part of antioxidant, 2.5 parts of biocompatible agent, 4 parts of heat-sealing auxiliary agent, 1.5 parts of toughening agent and 7 parts of inorganic filler;
the heat-sealing auxiliary agent comprises the following components in parts by weight: 3.9 parts of nonylphenol polyoxyethylene ether, 2 parts of diacetyl epoxy vegetable oil acid glyceride, 2 parts of acetyl tributyl citrate, 1.5 parts of 2, 2' - (1, 3-phenylene) -bisoxazoline and 1.2 parts of 2,2, 2-trifluoroethyl methacrylate.
3. The fully biodegradable bubble film according to any of claims 1-2, wherein said polylactic acid is made by the following method:
(1) mixing lactic acid with stannous chloride and p-toluenesulfonic acid at the temperature of 100-120 ℃ under a vacuum condition, heating to the temperature of 145-160 ℃ for reaction for 1-2h, adding pentaerythritol, heating to the temperature of 170-180 ℃ for reaction for 1-2h, wherein the mass ratio of polylactic acid to stannous chloride to p-toluenesulfonic acid is 1 (0.005-0.01) to (0.005-0.01), and the mass ratio of lactic acid to pentaerythritol is 1: 0.4-0.5;
(2) adding toluene into the product obtained in the step (1), heating to 90-100 ℃, adding acrylic acid, p-toluenesulfonic acid and hydroquinone, heating to 120-150 ℃, reacting for 3-5h, vacuumizing, washing with acetone to obtain a semi-finished product of polylactic acid, wherein the mass ratio of lactic acid to toluene is 1:2.5-3, the mass ratio of lactic acid to p-toluenesulfonic acid to hydroquinone is 3 (0.01-0.03) to (0.003-0.005), and the mass ratio of acrylic acid to pentaerythritol is 3-5: 1;
(3) mixing 2.3-4.5 parts of stearic acid, 1.2-2.4 parts of titanate coupling agent and 8-12 parts of water by weight to prepare a mixed solution, putting 4.6-5.8 parts of nano calcium carbonate and 3.8-4.6 parts of nano silicon dioxide into the mixed solution, stirring for 3-5h, drying 10-15 parts of semi-finished polylactic acid at 70-80 ℃ for 6-8h, putting into 10-15 parts of polyethylene glycol with the mass concentration of 5%, adding pretreated nano calcium carbonate and nano silicon dioxide, mixing, extruding and granulating.
4. The fully biodegradable bubble film according to any one of claims 1-2, wherein the inorganic filler is calcium carbonate, talc and glass powder in a mass ratio of 5:1.7-2.3: 1.3-1.8.
5. The fully biodegradable bubble film according to any one of claims 1-2, wherein the antioxidant comprises 2,2, 4-trimethyl-1, 2-dihydroquinoline, alkylaryl phosphite and nonylphenol polyoxyethylene ether phosphate, and the mass ratio of 2,2, 4-trimethyl-1, 2-dihydroquinoline, alkylaryl phosphite and nonylphenol polyoxyethylene ether phosphate is 1:1.3-1.6: 0.8-1.2.
6. The fully biodegradable bubble film according to any one of claims 1-2, wherein the thickness of the bubble layer is 0.02-0.06mm, and the thickness of the surface layer and the inner layer is 0.015-0.035 mm; the bubble diameter of the bubbles in the bubble film is 8-12mm, and the bubble height is 3-5 mm.
7. The fully biodegradable bubble film according to any one of claims 1-2, wherein the raw materials of the surface layer, the bubble layer and the inner layer further comprise the following components in parts by weight: 3.2-4.5 parts of degradable polyurethane, 1.4-2 parts of expanded starch and 1.2-2.4 parts of straw plant fiber.
8. The fully biodegradable bubble film according to claim 7, wherein said degradable polyurethane is prepared by a method comprising: drying 3-5 parts of bark of black wattle at 110 ℃ for 22-24h, crushing, adding into 6-10 parts of polyether polyol, stirring uniformly at high speed, sealing, standing at room temperature for 1-2d, adding 0.5-1 part of dibutyl tin dilaurate and 1-1.5 parts of silicone oil, mixing uniformly, adding 0.5-1 part of diphenylmethane diisocyanate under stirring at high speed, stirring for 1-2h, pouring into a mold preheated at 60-70 ℃ for 10-15min, standing at room temperature for 1-2h, taking out the mold, curing at room temperature for 7-10d, and crushing to obtain the particle size of 5-10 um.
9. A process for preparing a fully biodegradable bubble film according to any one of claims 1 to 8, comprising the following steps:
s1, preparing the surface layer, the bubble layer and the inner layer into granules according to the following method: drying polylactic acid and poly (butylene adipate-terephthalate) at 60-90 ℃ for 2-8h, adding a biological compatilizer, a flexibilizer, a heat-sealing auxiliary agent, an inorganic filler, an antioxidant, degradable polyurethane, expanded starch and straw plant fibers, uniformly mixing, adding into a double-screw extruder, and extruding and granulating to obtain granules;
s2, adding the inner layer granules and the bubble layer granules into a casting machine, extruding and casting to prepare an inner layer diaphragm and a bubble layer diaphragm, forming bubbles on the bubble layer diaphragm through a plastic suction bubble roller with the vacuum degree of 0.04-0.06MPa, and compounding the bubbles and the inner layer diaphragm through a compounding roller;
s3, extruding and casting the surface layer granules to form a surface layer membrane, and compounding the surface layer membrane with one side of the bubble layer with convex bubbles through a compounding roller to prepare the full-biodegradable bubble film.
10. The process for preparing fully biodegradable bubble films according to claim 9, wherein in the step S1, the temperature of the feeding section of the twin-screw extruder is as follows: 130 ℃ and 150 ℃, and the temperature of the plasticizing section: 170 ℃ and 190 ℃, and the temperature of the homogenization section: at the temperature of 200-; in the step S2, the extrusion temperature of the inner layer granules and the bubble layer granules is 200-250 ℃, and the composite pressure of the inner layer membrane and the bubble layer is 45-50kg/m2The compounding temperature is 55-80 ℃; the extrusion temperature of the surface layer granules in the step S3 is 170-190 ℃, and the composite pressure of the surface layer membrane and the bubble layer is 10-15kg/m2Then, it is repeatedThe resultant temperature is 50-70 ℃.
CN201911371303.3A 2019-12-27 2019-12-27 Full-biodegradable bubble film and preparation process thereof Withdrawn CN111114077A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911371303.3A CN111114077A (en) 2019-12-27 2019-12-27 Full-biodegradable bubble film and preparation process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911371303.3A CN111114077A (en) 2019-12-27 2019-12-27 Full-biodegradable bubble film and preparation process thereof

Publications (1)

Publication Number Publication Date
CN111114077A true CN111114077A (en) 2020-05-08

Family

ID=70503520

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911371303.3A Withdrawn CN111114077A (en) 2019-12-27 2019-12-27 Full-biodegradable bubble film and preparation process thereof

Country Status (1)

Country Link
CN (1) CN111114077A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662147A (en) * 2020-12-23 2021-04-16 青岛润兴塑料新材料有限公司 High-performance ternary compound biodegradable film
CN113500769A (en) * 2021-07-23 2021-10-15 厦门长塑实业有限公司 Biodegradable biaxially oriented composite film and preparation method and application thereof
CN114457458A (en) * 2022-02-18 2022-05-10 漳州遖扬新材料科技有限公司 Completely biodegradable dust screen and preparation method thereof
CN114479147A (en) * 2021-02-24 2022-05-13 陈雅婷 Degradable plastic composite film
CN115257112A (en) * 2022-06-07 2022-11-01 青岛周氏塑料包装有限公司 Multilayer biodegradable air bubble film and preparation process thereof
CN115322539A (en) * 2022-06-27 2022-11-11 广东春夏新材料科技股份有限公司 Polylactic acid composite material and preparation method thereof
CN115449199A (en) * 2022-10-15 2022-12-09 深圳市鼎力盛科技有限公司 Novel polymer material bacterium-resistant plastic bubble bag and preparation method thereof
CN116589731A (en) * 2023-04-03 2023-08-15 嘉兴高正新材料科技股份有限公司 Degradable multilayer composite bubble film and preparation method thereof
CN117719234A (en) * 2024-02-09 2024-03-19 新航涂布科技(苏州)有限公司 High-temperature-resistant stretch-resistant film and preparation method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662147A (en) * 2020-12-23 2021-04-16 青岛润兴塑料新材料有限公司 High-performance ternary compound biodegradable film
CN114479147A (en) * 2021-02-24 2022-05-13 陈雅婷 Degradable plastic composite film
CN113500769A (en) * 2021-07-23 2021-10-15 厦门长塑实业有限公司 Biodegradable biaxially oriented composite film and preparation method and application thereof
CN114457458A (en) * 2022-02-18 2022-05-10 漳州遖扬新材料科技有限公司 Completely biodegradable dust screen and preparation method thereof
CN115257112A (en) * 2022-06-07 2022-11-01 青岛周氏塑料包装有限公司 Multilayer biodegradable air bubble film and preparation process thereof
CN115257112B (en) * 2022-06-07 2024-04-05 青岛周氏塑料包装有限公司 Multilayer biodegradable bubble film and preparation process thereof
CN115322539A (en) * 2022-06-27 2022-11-11 广东春夏新材料科技股份有限公司 Polylactic acid composite material and preparation method thereof
CN115449199A (en) * 2022-10-15 2022-12-09 深圳市鼎力盛科技有限公司 Novel polymer material bacterium-resistant plastic bubble bag and preparation method thereof
CN115449199B (en) * 2022-10-15 2023-09-08 深圳市鼎力盛科技有限公司 High-molecular material antibacterial plastic bubble bag and preparation method thereof
CN116589731A (en) * 2023-04-03 2023-08-15 嘉兴高正新材料科技股份有限公司 Degradable multilayer composite bubble film and preparation method thereof
CN116589731B (en) * 2023-04-03 2024-03-15 嘉兴高正新材料科技股份有限公司 Degradable multilayer composite bubble film and preparation method thereof
CN117719234A (en) * 2024-02-09 2024-03-19 新航涂布科技(苏州)有限公司 High-temperature-resistant stretch-resistant film and preparation method thereof

Similar Documents

Publication Publication Date Title
CN111114077A (en) Full-biodegradable bubble film and preparation process thereof
CN110091564B (en) Full-biological 100% full-degradable composite membrane and processing technology and application thereof
CN110341271A (en) A kind of high strength Fully-biodegradable composite membrane and its production technology and application
CN103540111B (en) A kind of high intensity, resistant to elevated temperatures fully-degradable polylactic acid sheet material and manufacture method thereof
JP2527523B2 (en) Biodegradable polymer composition based on starch and thermoplastic polymer
CN108822514B (en) Completely biodegradable polylactic acid based blown film and preparation method thereof
CN112606511B (en) High-barrier degradable biaxially oriented film and preparation method thereof
CN104371296B (en) Poly-methyl ethylene carbonate composition and preparation method thereof
CN107603168B (en) Polylactic acid-based film and preparation method thereof
CN104109262B (en) A kind of thermoplastic starch-polyvinyl alcohol composite plastic film
CN113956630A (en) Completely biodegradable film and preparation method thereof
CN103224697B (en) PHA/PCL blend of a kind of fully biodegradable and preparation method thereof
CN111234481A (en) Preparation method of high-toughness low-cost polylactic acid composite material
CN111907031B (en) PLA/PBAT film, preparation method and application
WO2020088214A1 (en) Pha-modified tps/pbat biodegradable resin and preparation method therefor
CN111548617B (en) Biodegradable polylactic acid material and preparation method and application thereof
CN113442401A (en) High-strength high-barrier PGA/PBAT food packaging film and preparation method thereof
CN115594957B (en) High-barrier degradable material, high-barrier degradable film and preparation method thereof
CN102311622B (en) Modified polylactic acid material for disposable syringe
US20230303829A1 (en) Biodegradable material, preparation method and application thereof
JP2000015765A (en) Biodegradable multilayer film sheet
CN114605798A (en) Production process of degradable high polymer material film
Toh et al. Influence of compounding methods on poly (vinyl) alcohol/sago pith waste biocomposites: mechanical and water absorption properties
CN115593061A (en) High-barrier biodegradable composite membrane and preparation process thereof
CN115707575A (en) Multilayer film and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20200508

WW01 Invention patent application withdrawn after publication