CN109177401B - Completely biodegradable blown film, preparation method and application thereof - Google Patents

Completely biodegradable blown film, preparation method and application thereof Download PDF

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CN109177401B
CN109177401B CN201810843532.XA CN201810843532A CN109177401B CN 109177401 B CN109177401 B CN 109177401B CN 201810843532 A CN201810843532 A CN 201810843532A CN 109177401 B CN109177401 B CN 109177401B
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parts
film
chain extender
zones
compatibilizer
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CN109177401A (en
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张会良
边俊甲
杨佳
金宝昌
贾世玲
杨慧丽
韩立晶
董丽松
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • 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
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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

Abstract

The invention provides a completely biodegradable blown film, a preparation method and application thereof, wherein the film comprises an inner layer, a middle layer and an outer layer which are contacted in sequence; the inner layer comprises polylactic acid, polybutylene terephthalate-adipate, talcum powder, an opening agent and carbon black in parts by weight; the middle layer and the outer layer both comprise polylactic acid, poly terephthalic acid-adipic acid-butanediol ester and titanium dioxide; the three layers also respectively comprise glycerol monostearate, acetyl tributyl citrate, ethylene bis stearamide and a chain extender; the opening agent is erucamide or oleamide; the chain extender is a copolymer of styrene-acrylic acid-glycidyl methacrylate and/or a copolymer of styrene-maleic anhydride-glycidyl methacrylate. The film has high tensile elongation at break, pendulum impact strength, tensile strength, Young's modulus and heat seal strength, and retains complete biodegradability.

Description

Completely biodegradable blown film, preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a completely biodegradable blown film, a preparation method and application thereof.
Background
Unlike conventional petroleum-based plastics, poly (butylene terephthalate-adipate) is an aliphatic aromatic copolyester made from petroleum-based resources, and consists of two comonomers, one is a rigid BT segment (butylene terephthalate) consisting of terephthalic acid and 1, 4-butanediol monomers, and the other is a flexible BA segment (butylene adipate) consisting of adipic acid and 1, 4-butanediol monomers. PBAT has the degradability of aliphatic polyester and the better mechanical property of aromatic polyester.
Polylactic acid (PLA) is polymerized from lactic acid obtained by fermenting plant starch, is a renewable resource, has biodegradation characteristics, and has very important significance for protecting environment. Under the situation that petroleum energy is increasingly tense, development and research of PLA resin are particularly important. PLA by itself has properties similar to general purpose plastic polypropylene, such as high modulus, high tensile strength and good processability. However, PLA is very brittle and has an impact strength of less than 5KJ/m2Severely limiting its widespread use.
Therefore, modification research is actively carried out at home and abroad aiming at the defect of serious brittleness of PLA, the method for improving the toughness of the PLA by adopting multi-component blending modification is the main technical means at present, and how to obtain the PLA resin with high toughness and biodegradability is the requirement for preparing products such as degradable packaging films and the like.
PBAT is biodegradable, has a tensile elongation at break of up to around 700% and a low modulus of elasticity, and is therefore considered to be a good choice for toughening PLA. Their blends are still biodegradable and can theoretically have the high strength of PLA and the high ductility and toughness of PBAT, respectively. However, simple mixing of PLA with other components often does not produce satisfactory performance because there is generally a thermodynamic incompatibility between the two components due to unfavorable interactions between the molecular segments of the components resulting in their immiscibility or poor interfacial adhesion. To improve the compatibility of the polymer blend and increase the interfacial adhesion between the matrix and the dispersed phase, reactive compatibilization or the addition of compatibilizers are often used to increase the compatibility to achieve the desired properties.
A biodegradable film and a preparation method thereof are disclosed in world invention patent WO2018/028513A1 disclosed by bear King et al, and the method comprises the steps of extruding PBAT, PLA, talcum powder or calcium carbonate and epoxy copolymer by a double screw, and then carrying out blow molding processing to prepare the biodegradable blown film with balanced longitudinal and transverse tearing strength.
The Chinese patent with application number 201710167009.5 of Qinsheng et al discloses an enhanced full-biodegradable material and a preparation method thereof, wherein PBAT, PLA, carbon nanotubes, silane or titanate coupling agent are extruded by twin screws and then blow-molded, so that the tensile strength and elongation at break of the film can be remarkably improved.
The Chinese patent with application numbers of 201710572627.8 and 201710572630.X of Miqinghua et al discloses an ultrathin transparent full-biodegradable film blowing-film-grade material and a preparation method thereof, wherein PBAT, PLA, a reinforcing, toughening and permeability-increasing agent and a reinforcing, toughening and permeability-increasing agent can be selected from inorganic hydrophobic nano-silica, or one or more of organic Axma-8900 or ADX-1200s resin compatilizer or Hangzhou Ike CE-AZ01 compatilizer, and then the materials are extruded by twin screws and processed by blow molding to obtain the ultrathin and ultra-transparent full-biodegradable film with the thickness of 5 microns, and the ultrathin and ultra-transparent full-biodegradable film can be used for packaging films, shopping bags and mulching films.
Weraporn Pivsa-Art et al in journal Energy Procedia (2011,9: 581-.
Jeff Schneider et al reported lactide-epoxy modified PLA/PBAT films in Journal of Applied Polymer Science (2016, DOI:10.1002/APP.43310.) and showed that the modified films had good physical and mechanical properties.
Worasak Phytwarotai et al reported in Journal of Thermal Analysis and Calcalorimetry (2016,126: 1797. RTM. 1808.) that PLA, PBAT, Talc as a nucleating agent (Talc), and diphenylmethane diisocyanate (MDI) as a compatibilizer were blended and blown into films at ratios of 100/0/0/0, 90/10/0/0, 90/10/1/0, 90/10/1/1, 90/10/1/3, 90/10/1/5, 90/10/1/7 for PLA/PBAT/Talc/MDI (phr/phr/phr), respectively, and the results showed that Talc was a good nucleating agent for PLA, and the addition of Talc and PBAT greatly increased the nucleation rate for PLA, however, the addition of the compatibilizer MDI, and the formation of more long chain compounds, will hinder the crystallization behavior of PLA.
Sutinee Girdtheop et al, in the Journal European Polymer Journal (2016,82: 244-.
Stroc et al, journal "plastics technology" (2015,43 (10): 68-72.) reported that dibenzoyl peroxide (BOP) was used as an interfacial compatibilizer, and PLA and PBAT were blended, extruded and blown into films with ratios of (phr/phr/phr) of 55/45/0.5/1, 45/55/0.5/1, and 35/65/0.5/1, respectively, to the antioxidant 1010/BOP, indicating that the films had strong tensile strength and tear strength, and had good elongation at break when the PBAT was increased to some extent.
On the premise of advocating green environmental protection and improving ecological environment in the current world, the biodegradable film has wide development space. The development trend of the polylactic acid film field in the future is to modify polylactic acid and research and produce biodegradable films with better performance and lower price.
Disclosure of Invention
In view of the above, the present invention aims to provide a completely biodegradable blown film, which has a high tensile elongation at break and a high charpy impact strength, a process for its preparation and its use.
The invention provides a completely biodegradable blown film, which comprises an inner layer, a middle layer and an outer layer which are contacted in sequence;
the inner layer comprises, by weight, 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent, 0.1-2 parts of a lubricant and 0.2-2 parts of carbon black;
the middle layer comprises 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide;
the outer layer comprises 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide;
the compatibilizer is glycerol monostearate; the plasticizer is acetyl tributyl citrate; the lubricant is ethylene bis stearamide; the opening agent is erucamide or oleamide; the nucleating agent is talcum powder; the chain extender is a copolymer of styrene-acrylic acid-glycidyl methacrylate and/or a copolymer of styrene-maleic anhydride-glycidyl methacrylate.
Preferably, the thickness of the completely biodegradable blown film is 0.05-0.06 mm.
Preferably, the polylactic acid is polylactic acid of type REVODE 110;
the polybutylene terephthalate adipate is polybutylene terephthalate with the model number TH 801T.
Preferably, the type of the chain extender is ADR4368 and/or ADR 4370.
The invention provides a preparation method of a completely biodegradable blown film, which comprises the following steps:
mixing 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent and 0.2-2 parts of carbon black, melting, extruding and granulating to obtain inner layer resin;
mixing 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide, melting, extruding and granulating to obtain middle layer resin;
mixing 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide, melting, extruding and granulating to obtain outer layer resin;
and co-extruding the inner layer resin, the middle layer resin and the outer layer resin, and performing blow molding to form a film, thereby obtaining the completely biodegradable blown film.
Preferably, the temperature of the extrusion granulation is: a first area: 120-140 ℃, and a second zone: 150-170 ℃, three areas: 160-180 ℃, four zones: 170-190 ℃, and five zones: 170-190 ℃, and six zones: 170-190 ℃, seven areas: 170-190 ℃, eight zones: 170-190 ℃, nine areas: 170-190 ℃, ten areas: 170-190 ℃, head: 170-190 ℃.
Preferably, when the film is formed by blow molding, the temperature of the inner layer is as follows: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
the set temperature of the middle layer is as follows: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
the set temperature of the outer layer is: a first area: 155 ℃ and 160 ℃, and the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃.
The invention provides a complete biodegradable bag which is prepared from the complete biodegradable film prepared by the preparation method of the technical scheme or the complete biodegradable film prepared by the preparation method of the technical scheme.
The invention provides a completely biodegradable blown film, which comprises an inner layer, a middle layer and an outer layer which are contacted in sequence; the inner layer comprises, by weight, 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent, 0.1-2 parts of a lubricant and 0.2-2 parts of carbon black; the middle layer comprises 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide; the outer layer comprises 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide; the compatibilizer is glycerol monostearate; the plasticizer is acetyl tributyl citrate; the lubricant is ethylene bis stearamide; the opening agent is erucamide or oleamide; the nucleating agent is talcum powder; the chain extender is a copolymer of styrene-acrylic acid-glycidyl methacrylate and/or a copolymer of styrene-maleic anhydride-glycidyl methacrylate. According to the invention, the poly (terephthalic acid) -butanediol adipate is used as a toughening agent of polylactic acid, the glyceryl monostearate is used as a compatibilizer, the copolymer of styrene-acrylic acid-epoxypropyl methacrylate and/or the copolymer of styrene-maleic anhydride-epoxypropyl methacrylate is used as a chain extender, and an auxiliary agent is added, so that the tensile breaking elongation and the pendulum impact strength of the completely biodegradable blown film can be effectively improved by synergistic use. The synergistic use of the chain extender and the compatibilizer can improve the melt strength of the film, ensure the processibility fluidity of the film and improve the dispersibility of the titanium dioxide or the carbon black in the PLA/PBAT blown film resin under the synergistic effect of other additives. The film also has high tensile strength, Young's modulus and heat seal strength, and retains full biodegradation characteristics. The experimental results show that: the transverse tensile strength is 20.3-23.7 MPa, and the longitudinal tensile strength is 27.4-33.6 MPa; the transverse elongation at break is 310.9-560.7%, and the longitudinal elongation at break is 169.8-284.1%; the transverse Young modulus is 393.7-782.4 MPa, and the longitudinal Young modulus is 541.8-1182.3 MPa; the transverse right-angle tear strength is 65.6-113.7 KN/m, and the longitudinal right-angle tear strength is 85.9-121.4 KN/m; the heat seal strength is 21.3-26.1N/15 mm; the impact strength of the pendulum bob is 0.82-1.18J.
Detailed Description
The invention provides a completely biodegradable blown film, which comprises an inner layer, a middle layer and an outer layer which are contacted in sequence;
the inner layer comprises, by weight, 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent, 0.1-2 parts of a lubricant and 0.2-2 parts of carbon black;
the middle layer comprises 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide;
the outer layer comprises 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide;
the compatibilizer is glycerol monostearate; the plasticizer is acetyl tributyl citrate; the lubricant is ethylene bis stearamide; the opening agent is erucamide or oleamide; the nucleating agent is talcum powder; the chain extender is a copolymer of styrene-acrylic acid-glycidyl methacrylate (ADR-4368) and/or a copolymer of styrene-maleic anhydride-glycidyl methacrylate (ADR-4370).
According to the invention, the poly (terephthalic acid) -butanediol adipate is used as a toughening agent of polylactic acid, the glyceryl monostearate is used as a compatibilizer, the copolymer of styrene-acrylic acid-epoxypropyl methacrylate and/or the copolymer of styrene-maleic anhydride-epoxypropyl methacrylate is used as a chain extender, and an auxiliary agent is added, so that the tensile breaking elongation and the pendulum impact strength of the completely biodegradable blown film can be effectively improved by synergistic use. The synergistic use of the chain extender and the compatibilizer can improve the melt strength of the film, ensure the processibility fluidity of the film and improve the dispersibility of the titanium dioxide or the carbon black in the PLA/PBAT blown film resin under the synergistic effect of other additives.
In the present invention, the polylactic acid is preferably of type REVODE 110. The polybutylene terephthalate-adipate is preferably polybutylene terephthalate-adipate with the model number TH 801T.
In the invention, the polybutylene terephthalate-adipate-terephthalate (PBAT) is a copolyester of adipic acid and terephthalic acid and butanediol, has the characteristics of polybutylene adipate (PBA) and polybutylene terephthalate (PBT), has better ductility and elongation at break, better heat resistance and impact property and excellent biodegradability, and is one of degradation materials which are very active in the research of the current biodegradable plastics and are best in market application. But the compatibility of PBAT and polylactic acid PLA is poor, entanglement among molecular chains is lacked, phase separation is easy to occur in the film blowing processing process, and the transverse tensile strength of the film is insufficient, so that the film bubble of the blown film is cracked.
In the invention, the compatibilizer is Glycerol Monostearate (GMS) which is yellowish waxy solid or flake, contains a small amount of diester and triester besides monoester, and is tasteless, odorless and nontoxic; the chemical structure of the blend has hydrophilic hydroxyl and lipophilic long-chain alkyl functional groups, so that the compatibility of PLA and PBAT can be improved, the functions of a compatibilizer and a lubricant are achieved, the viscosity of the PLA/PBAT blend is favorably reduced, the processing fluidity of the blend system is improved, particularly the fluidity of a melt in the process of pulling the melt from a die head of a film blowing machine in the film blowing processing process is improved, and the melt strength and the melt flow rate are controlled in a reasonable and effective film blowing processing range.
In the invention, the chain extender is a copolymer of styrene-acrylic acid-glycidyl methacrylate and/or a copolymer of styrene-maleic anhydride-glycidyl methacrylate; the chain extender contains epoxy functional groups, can react with terminal hydroxyl and carboxyl of PBAT and PLA and is combined with multifunctional additives at the tail ends of different macromolecular fragments (carboxyl and hydroxyl in polyester), so that a polymer molecular chain is prolonged, the average molar mass of the polymer is increased, and the chain extender can also be used as a reactive compatibilizer in a blend to connect the PLA and the PBAT molecular chains together, improve the entanglement of the PLA and the PBAT molecular chains, improve the melt strength and viscosity of the PLA/PBAT blend and improve the compatibility of the PLA and the PBAT.
The chain extender and the compatibilizer GMS are used cooperatively, so that the melt strength of a blending system is improved, the processable fluidity of the film is ensured, and the dispersibility of the titanium dioxide or the carbon black in the PLA/PBAT blown film resin is improved under the synergistic effect of other additives.
In the present invention, the plasticizer is acetyl tributyl citrate (ATBC). The plasticizer can effectively improve the tensile elongation at break and the pendulum impact strength resistance of the polylactic acid film, maintains the flexibility of the film, and solves the brittleness defect of the express bag film.
In the invention, the lubricant is ethylene bis stearamide, which is beneficial to the extrusion of the special modified polylactic acid blown film resin and the blow molding processing of a blown film, and improves the surface smoothness of the film.
In the present invention, the opening agent is Erucamide (EA) or oleamide; the opening agent can improve the opening property of the film and avoid the mutual adhesion of two layers of films caused in the rolling and winding process of the blown film.
The nucleating agent is talcum powder. The talcum powder is an environment-friendly auxiliary agent with excellent performance and low price; the talcum powder added into the plastic film can be used as an efficient nucleating agent of polylactic acid, reduces the size of crystal grains of the polylactic acid, improves the crystal nucleus density, improves the strength and the heat resistance of the film, and also obviously improves the waterproof performance and the ageing resistance.
In the invention, the carbon black is used for improving the light resistance of the express bag film, avoiding visible light transmission and protecting the safety of mails. Titanium white powder can improve the white of film, shields express bag inner layer black simultaneously, is favorable to improving express bag outward appearance aesthetic property.
In the invention, the thickness of the completely biodegradable blown film is preferably 0.05-0.06 mm.
The completely biodegradable blown film is a completely biodegradable film with an outer layer of grey white and an inner layer of black. All components used by the film can be completely biodegraded, the film has wide application field, can replace PE to be made into various environment-friendly express packaging bags, and has wide market prospect. The industrialization of the biodegradable material and the express bag is beneficial to the long-term development of energy and material resources, solves the white pollution, promotes the development of the novel environment-friendly material industry, and has great economic and social significance.
The invention provides a preparation method of a completely biodegradable blown film, which comprises the following steps:
mixing 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent and 0.2-2 parts of carbon black, melting, extruding and granulating to obtain inner layer resin;
mixing 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide, melting, extruding and granulating to obtain middle layer resin;
mixing 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide, melting, extruding and granulating to obtain outer layer resin;
and co-extruding the inner layer resin, the middle layer resin and the outer layer resin, and performing blow molding to form a film, thereby obtaining the completely biodegradable blown film.
In the invention, the inner layer resin, the middle layer resin and the outer layer resin are extruded and granulated by a double-screw extruder; when extruding and granulating, the set temperature of the double-screw extruder is as follows: a first area: 120-140 ℃, and a second zone: 150-170 ℃, three areas: 160-180 ℃, four zones: 170-190 ℃, and five zones: 170-190 ℃, and six zones: 170-190 ℃, seven areas: 170-190 ℃, eight zones: 170-190 ℃, nine areas: 170-190 ℃, ten areas: 170-190 ℃, head: 170-190 ℃, screw rotation speed: 200 to 400 rpm.
And a film forming machine is adopted for blow molding film formation. When the film is formed by blow molding, the set temperature of the film blowing machine is as follows:
inner layer: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
middle layer: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
outer layer: a first area: 155 ℃ and 160 ℃, and the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
a mould body: 160-175 ℃; die opening: 160-175 ℃;
inner layer screw rotation speed: 50-300 rpm, middle layer screw rotation speed: 50-300 rpm, outer layer screw rotation speed: 50-300 rpm, a traction speed of 10-20 m/min and a blow-up ratio of 2-6.
The invention adopts a three-layer co-extrusion technology, reasonably optimizes the composition proportion of PLA and PBAT of each layer, ensures that the composition proportion of PLA and PBAT of the inner, middle and outer three layers is in a relatively approximate range, and avoids the layering phenomenon among the layers; and multiple auxiliaries are used for synergistic action, the consistency of the film blowing temperature and the melt strength in the co-extrusion film blowing process of each layer during film blowing processing is ensured, and the mechanical property of the film is favorably ensured.
The invention provides a complete biodegradable bag which is prepared from the complete biodegradable film prepared by the preparation method of the technical scheme or the complete biodegradable film prepared by the preparation method of the technical scheme.
In the present invention, the method for preparing the complete biodegradable bag preferably comprises the steps of:
printing and rolling the completely biodegradable film to obtain a printed film;
and gluing the printed film in the traction process, synchronously covering the release film on the glue surface, and then performing thermal bonding and cutting to obtain the completely biodegradable bag.
In the invention, the printed film is coated with glue through a glue applying opening in the drawing process, the edge of the film is coated with sealing glue, and simultaneously, the parting film covers the glue surface on the glue surface coated with the sealing glue. The heat sealing temperature is preferably 300-400 ℃; the cutting speed is preferably 100-150 pieces/min.
In order to further illustrate the present invention, a fully biodegradable film, a method for preparing the same, and applications thereof, which are provided by the present invention, will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
PLA in the following examples was purchased from Zhejiang Haizhen biomaterial, Inc. under model REVODE 110; PBAT is purchased from polyester Co., Ltd, blue Shantun, Xinjiang, and has the model number TH 801T; the chain extender is purchased from BASF company and has the model number of ADR-4370 or ADR-4368. The tensile properties of the films in the following examples were tested according to the GB/T1010.3-2006 standard; the tear strength was tested according to QB/T1130-91; the heat seal strength was measured according to ASTM F88-05.
Example 1
The invention provides a completely biodegradable film, which comprises the following components in parts by weight:
inner layer resin: 20 parts of PLA; 71.25 parts of PBAT; 0.6 part of carbon black; 2 parts of a compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 1 parts of an opening agent EA; chain extender 4370 type ADR 0.15 portion; 2 parts of nucleating agent talcum powder.
Weighing PLA, PBAT, carbon black, GMS, ATBC, EA, EBS, ADR and talcum powder according to the formula, mechanically blending the components for 5 minutes, adding the mixed raw materials into a double-screw extruder, and carrying out extrusion granulation under the conditions of: the set temperature of the twin-screw extruder is as follows: a first area: 120-140 ℃, and a second zone: 150-170 ℃, three areas: 160-180 ℃, four zones: 170-190 ℃, and five zones: 170-190 ℃, and six zones: 170-190 ℃, seven areas: 170-190 ℃, eight zones: 170-190 ℃, head: 170-190 ℃, screw rotation speed: 100 to 300 rpm.
Middle layer resin: 20 parts of PLA; 64.95 parts of PBAT; 10 parts of titanium dioxide; 1 part of a compatibilizer GMS; 3 parts of plasticizer ATBC; 1 part of lubricant EBS; chain extender 4370 type ADR0.05 portion;
weighing PLA, PBAT, titanium dioxide, GMS, ATBC, EBS and ADR according to the formula, mechanically blending the components for 5 minutes, adding the mixed raw materials into a double-screw extruder, and carrying out extrusion granulation under the following conditions: the set temperature of the twin-screw extruder is as follows: a first area: 120-140 ℃, and a second zone: 150-170 ℃, three areas: 160-180 ℃, four zones: 170-190 ℃, and five zones: 170-190 ℃, and six zones: 170-190 ℃, seven areas: 170-190 ℃, eight zones: 170-190 ℃, head: 170-190 ℃, screw rotation speed: 100 to 300 rpm.
Outer layer resin: 25 parts of PLA; 66.8 parts of PBAT; 4 parts of titanium dioxide; 1 part of a compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.2 part of chain extender 4370 type ADR;
weighing PLA, PBAT, titanium dioxide, GMS, ATBC, EBS and ADR according to the formula, mechanically blending the components for 5 minutes, adding the mixed raw materials into a double-screw extruder, and carrying out extrusion granulation under the following conditions: the set temperature of the twin-screw extruder is as follows: a first area: 120-140 ℃, and a second zone: 150-170 ℃, three areas: 160-180 ℃, four zones: 170-190 ℃, and five zones: 170-190 ℃, and six zones: 170-190 ℃, seven areas: 170-190 ℃, eight zones: 170-190 ℃, head: 170-190 ℃, screw rotation speed: 100 to 300 rpm.
And respectively carrying out air blast drying on the obtained special resin for the inner layer, the middle layer and the outer layer of the film blowing in a constant-temperature oven at the temperature of 80 ℃ for 5 hours, and then respectively adding the special resin into an inner hopper, a middle hopper and an outer hopper of a three-layer co-extrusion film blowing machine.
The set temperature of the film blowing machine is as follows:
inner layer: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
middle layer: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
outer layer: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
a mould body: 160-175 ℃; die opening: 160-175 ℃.
Inner layer screw rotation speed: 50-300 rpm, middle layer screw rotation speed: 50-300 rpm, outer layer screw rotation speed: 50-300 rpm, a traction speed of 10-20 m/min, and a blow-up ratio of 2-6.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 1.
TABLE 1 Performance test results of completely biodegradable films prepared in examples 1 to 5 of the present invention
Figure BDA0001746132920000111
As can be seen from table 1: by adopting the express bag film provided by the invention, the tensile elongation at break and the pendulum impact strength of the blend can be improved along with the increase of the content of PBAT, but the tensile strength, Young modulus and tear strength of the blend are reduced to a certain extent.
Example 2:
the invention provides a completely biodegradable film, which comprises the following components in parts by weight:
inner layer resin: 10 parts of PLA; 81.9 parts of PBAT; 0.6 part of carbon black; 1 part of a compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 1 parts of an opening agent EA; 0.1 part of chain extender 4368 type ADR; 2.4 parts of nucleating agent talcum powder.
Middle layer resin: 10 parts of PLA; 74.9 parts of PBAT; 10 parts of titanium dioxide; 1 part of a compatibilizer GMS; 3 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.1 part of chain extender 4368 type ADR.
Outer layer resin: 15 parts of PLA; 76.3 parts of PBAT; 4 parts of titanium dioxide; 0.5 part of compatibilizer GMS; 3 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.2 part of chain extender 4368 type ADR.
The compounding and processing conditions of the inner, middle and outer layers of blown film resin were the same as in example 1.
The set temperature of the film blowing machine was the same as in example 1.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 1.
Example 3:
the invention provides a completely biodegradable film, which comprises the following components in parts by weight:
inner layer resin: 25 parts of PLA; 66.85 parts of PBAT; 0.6 part of carbon black; 1 part of a compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 1 part of an opening agent EA; chain extender 4370 type ADR 0.15 portion; 2.4 parts of nucleating agent talcum powder.
Middle layer resin: 25 parts of PLA; 58.9 parts of PBAT; 10 parts of titanium dioxide; 1 part of a compatibilizer GMS; 4 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.1 part of chain extender 4370 type ADR;
outer layer resin: 30 parts of PLA; 60.3 parts of PBAT; 4 parts of titanium dioxide; 0.5 part of compatibilizer GMS; 4 parts of plasticizer ATBC; 1 part of lubricant EBS; and 0.2 part of chain extender 4370 type ADR.
The compounding and processing conditions of the blown film resins for the inner layer, middle layer and outer layer were the same as in example 1.
The set temperature of the film blowing machine was the same as in example 1.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 1.
Example 4:
the invention provides a completely biodegradable film, which comprises the following components in parts by weight:
inner layer resin: 15 parts of PLA; 77.7 parts of PBAT; 0.6 part of carbon black; 0.5 part of compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 1 parts of an opening agent EA; 0.2 part of chain extender 4370 type ADR; 2 parts of nucleating agent talcum powder.
Middle layer resin: 20 parts of PLA; 61.8 parts of PBAT; 12 parts of titanium dioxide; 1 part of a compatibilizer GMS; 4 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.2 part of chain extender 4370 type ADR;
outer layer resin: 20 parts of PLA; 70.9 parts of PBAT; 4 parts of titanium dioxide; 1 part of a compatibilizer GMS; 3 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.1 part of chain extender 4370 type ADR.
The compounding and processing conditions of the blown film resins for the inner layer, middle layer and outer layer were the same as in example 1.
The set temperature of the film blowing machine was the same as in example 1.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 1.
Example 5:
the invention provides a completely biodegradable film, which comprises the following components in parts by weight:
inner layer resin: 15 parts of PLA; 76.85 parts of PBAT; 0.6 part of carbon black; 1 part of a compatibilizer GMS; 3 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.5 part of an opening agent EA; chain extender 4370 type ADR0.05 portion; 2 parts of nucleating agent talcum powder.
Middle layer resin: 20 parts of PLA; 65.3 parts of PBAT; 10 parts of titanium dioxide; 0.5 part of compatibilizer GMS; 3 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.2 part of chain extender 4370 type ADR;
outer layer resin: 25 parts of PLA; 66.9 parts of PBAT; 4 parts of titanium dioxide; 1 part of a compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 0.1 part of chain extender 4370 type ADR.
The compounding and processing conditions of the inner, middle and outer layer blown film resins were the same as in example 1.
The set temperature of the film blowing machine was the same as in example 1.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 1.
Comparative example 1
Compared with the embodiment 5 of the invention, the plasticizer selects polyethylene glycol to replace acetyl tributyl citrate, and the formula comprises the following components in parts by weight:
inner layer resin: 15 parts of PLA; 76.85 parts of PBAT; 0.6 part of carbon black; 1 part of a compatibilizer GMS; 3 parts of plasticizer polyethylene glycol (with the molecular weight of 1500 g/mol); 1 part of lubricant EBS; 0.5 part of an opening agent EA; chain extender 4370 type ADR0.05 portion; 2 parts of nucleating agent talcum powder.
Middle layer resin: 20 parts of PLA; 65.3 parts of PBAT; 10 parts of titanium dioxide; 0.5 part of compatibilizer GMS; 3 parts of plasticizer polyethylene glycol (with the molecular weight of 1500 g/mol); 1 part of lubricant EBS; 0.2 part of chain extender 4370 type ADR;
outer layer resin: 25 parts of PLA; 66.9 parts of PBAT; 4 parts of titanium dioxide; 1 part of a compatibilizer GMS; 2 parts of plasticizer polyethylene glycol (with the molecular weight of 1500 g/mol); 1 part of lubricant EBS; 0.1 part of chain extender 4370 type ADR.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 2.
Comparative example 2
As a comparative example of example 3, the fully biodegradable film of the present invention, in which the chain extender was removed from the formulation, had the following composition and weight ratio:
inner layer resin: 25 parts of PLA; 67 parts of PBAT; 0.6 part of carbon black; 1 part of a compatibilizer GMS; 2 parts of plasticizer ATBC; 1 part of lubricant EBS; 1 parts of an opening agent EA; 2.4 parts of nucleating agent talcum powder.
Middle layer resin: 25 parts of PLA; 59 parts of PBAT; 10 parts of titanium dioxide; 1 part of a compatibilizer GMS; 4 parts of plasticizer ATBC; 1 part of lubricant EBS;
outer layer resin: 30 parts of PLA; 60.5 parts of PBAT; 4 parts of titanium dioxide; 0.5 part of compatibilizer GMS; 4 parts of plasticizer ATBC; and 1 part of lubricant EBS.
The compounding and processing conditions of the blown film resins for the inner layer, middle layer and outer layer were the same as in example 1.
The set temperature of the film blowing machine was the same as in example 1.
The thickness of the film is controlled to be 0.05-0.06 mm, the mechanical property of the film is tested, and the test results are listed in Table 2.
TABLE 2 Performance test results for films prepared in comparative examples 1-2
Figure BDA0001746132920000141
From the analysis results of comparative example 1 and example 5, it can be found that the tensile strength, elongation at break, right angle tear strength, heat seal strength and pendulum impact strength of the film bag product are all reduced by about 10% only by changing the plasticizer from acetyl tributyl citrate to polyethylene glycol, which indicates that acetyl tributyl citrate has better plasticizing effect than polyethylene glycol in the blending system of the invention.
Compared with the analysis results of the comparative example 2 and the example 3, the results show that the tensile strength, the elongation at break and the pendulum impact strength of the right-angle tear strength of the film bag product are reduced by about 5-10% and the heat seal strength is reduced by about 20% after the chain extender 4370 type ADR is not added, which shows that the chain extender 4370 has a better chain extension effect in the blending system of the invention and can improve the comprehensive mechanical properties of the film bag.
From the above embodiments, the present invention provides a completely biodegradable blown film, comprising an inner layer, a middle layer and an outer layer in sequential contact; the inner layer comprises, by weight, 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent, 0.1-2 parts of a lubricant and 0.2-2 parts of carbon black; the middle layer comprises 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide; the outer layer comprises 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide; the compatibilizer is glycerol monostearate; the plasticizer is acetyl tributyl citrate; the lubricant is ethylene bis stearamide; the opening agent is erucamide or oleamide; the nucleating agent is talcum powder; the chain extender is a copolymer of styrene-acrylic acid-glycidyl methacrylate and/or a copolymer of styrene-maleic anhydride-glycidyl methacrylate. According to the invention, the poly (terephthalic acid) -butanediol adipate is used as a toughening agent of polylactic acid, the glyceryl monostearate is used as a compatibilizer, the copolymer of styrene-acrylic acid-epoxypropyl methacrylate and/or the copolymer of styrene-maleic anhydride-epoxypropyl methacrylate is used as a chain extender, and an auxiliary agent is added, so that the tensile breaking elongation and the pendulum impact strength of the completely biodegradable blown film can be effectively improved by synergistic use. The synergistic use of the chain extender and the compatibilizer can improve the melt strength of the film, ensure the processibility fluidity of the film and improve the dispersibility of the titanium dioxide or the carbon black in the PLA/PBAT blown film resin under the synergistic effect of other additives. The film also has high tensile strength, Young's modulus and heat seal strength, and retains full biodegradation characteristics. The experimental results show that: the transverse tensile strength is 20.3-23.7 MPa, and the longitudinal tensile strength is 27.4-33.6 MPa; the transverse elongation at break is 310.9-560.7%, and the longitudinal elongation at break is 169.8-284.1%; the transverse Young modulus is 393.7-782.4 MPa, and the longitudinal Young modulus is 541.8-1182.3 MPa; the transverse right-angle tear strength is 65.6-113.7 KN/m, and the longitudinal right-angle tear strength is 85.9-121.4 KN/m; the heat seal strength is 21.3-26.1N/15 mm; the impact strength of the pendulum bob is 0.82-1.18J.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A completely biodegradable blown film comprises an inner layer, a middle layer and an outer layer which are contacted in sequence;
the inner layer comprises, by weight, 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent, 0.1-2 parts of a lubricant and 0.2-2 parts of carbon black;
the middle layer comprises 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide;
the outer layer comprises 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate-butylene glycol ester, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide;
the compatibilizer is glycerol monostearate; the plasticizer is acetyl tributyl citrate; the lubricant is ethylene bis stearamide; the opening agent is erucamide or oleamide; the nucleating agent is talcum powder; the chain extender is a copolymer of styrene-acrylic acid-epoxypropyl methacrylate and/or a copolymer of styrene-maleic anhydride-epoxypropyl methacrylate;
the polylactic acid is polylactic acid with a model REVODE 110;
the polybutylene terephthalate-adipate is polybutylene terephthalate-adipate with the model number TH 801T; the model of the chain extender is ADR4368 and/or ADR 4370.
2. The fully biodegradable blown film according to claim 1, wherein said fully biodegradable blown film has a thickness of 0.05 to 0.06 mm.
3. A method for preparing a fully biodegradable blown film according to any one of claims 1 to 2, comprising the following steps:
mixing 10-25 parts of polylactic acid, 61.8-88.95 parts of polybutylene terephthalate-adipate, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-3 parts of a nucleating agent, 0.05-0.2 part of a chain extender, 0.1-1 part of an opening agent and 0.2-2 parts of carbon black, melting, extruding and granulating to obtain inner layer resin;
mixing 10-25 parts of polylactic acid, 52.8-83.25 parts of poly (terephthalic acid) -butanediol adipate, 0.1-2 parts of compatibilizer, 0.1-5 parts of plasticizer, 0.1-2 parts of lubricant, 0.05-0.2 part of chain extender and 6-12 parts of titanium dioxide, melting, extruding and granulating to obtain middle layer resin;
mixing 15-30 parts of polylactic acid, 53.8-82.65 parts of polybutylene terephthalate-adipate, 0.1-2 parts of a compatibilizer, 0.1-5 parts of a plasticizer, 0.1-2 parts of a lubricant, 0.05-0.2 part of a chain extender and 2-6 parts of titanium dioxide, melting, extruding and granulating to obtain outer layer resin;
and co-extruding the inner layer resin, the middle layer resin and the outer layer resin, and performing blow molding to form a film, thereby obtaining the completely biodegradable blown film.
4. The method according to claim 3, wherein the temperature of the extrusion granulation is: a first area: 120-140 ℃, and a second zone: 150-170 ℃, three areas: 160-180 ℃, four zones: 170-190 ℃, and five zones: 170-190 ℃, and six zones: 170-190 ℃, seven areas: 170-190 ℃, eight zones: 170-190 ℃, nine areas: 170-190 ℃, ten areas: 170-190 ℃, head: 170-190 ℃.
5. The production method according to claim 3, wherein the temperature of the inner layer when the film is blown into the film is: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
the set temperature of the middle layer is as follows: a first area: 155-160 ℃, and in the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃;
the set temperature of the outer layer is: a first area: 155 ℃ and 160 ℃, and the second zone: 165-170 ℃, three areas: 165-180 ℃, four zones: 165-180 ℃, five zones: 160-175 ℃.
6. A completely biodegradable bag, which is produced from the completely biodegradable film according to any one of claims 1 to 2 or the completely biodegradable film produced by the production method according to any one of claims 3 to 5.
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