WO2019052150A1 - 低成本生物基全降解薄膜及其制备方法 - Google Patents

低成本生物基全降解薄膜及其制备方法 Download PDF

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Publication number
WO2019052150A1
WO2019052150A1 PCT/CN2018/081023 CN2018081023W WO2019052150A1 WO 2019052150 A1 WO2019052150 A1 WO 2019052150A1 CN 2018081023 W CN2018081023 W CN 2018081023W WO 2019052150 A1 WO2019052150 A1 WO 2019052150A1
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Prior art keywords
parts
low
cost
bio
fully degradable
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PCT/CN2018/081023
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English (en)
French (fr)
Inventor
吴晓金
司鹏
吴维果
翁伟明
刘志刚
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江苏金聚合金材料有限公司
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Publication of WO2019052150A1 publication Critical patent/WO2019052150A1/zh
Priority to US16/851,056 priority Critical patent/US20200291225A1/en

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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the invention belongs to the technical field of fully biodegradable materials, relates to a biodegradable film, and more particularly to a low-cost bio-based fully degradable film and a preparation method thereof.
  • plastic packaging film has brought great convenience to our production and life.
  • the traditional plastic packaging film is made of non-degradable petroleum-based materials, its large use not only causes waste of resources, but also brings "white pollution" to the environment, which has aroused widespread concern in society. Incineration and in-situ burial of waste plastic film will cause serious air pollution and soil pollution, while secondary recycling has the disadvantages of low recovery rate, deterioration of material properties and high recycling cost. Therefore, the promotion of the use of fully biodegradable materials is undoubtedly It is an effective way to solve the problem of "white pollution” fundamentally.
  • the invention patent of CN102702696A is based on polylactic acid (PLA) and polybutylene adipate/butylene terephthalate (PBAT).
  • the prepared biodegradable film has a blown thickness of up to 20 ⁇ m, a tensile strength of 11 to 12.1 MPa, and an elongation at break of more than 150%.
  • the invention patent No. CN103589124A also prepares a PLA/PBAT whole organism. Degrade the film and increase the tensile strength of the film by up to 61 by adding a composite solubilizer and a mineral filler.
  • MPa MPa; the invention patent of CN102675839A is based on PLA, PBAT and polypropylene carbonate (PPC).
  • PPC polypropylene carbonate
  • the dart impact strength of the fully biodegradable film is higher than that of the conventional polyethylene film. All of the above biodegradable films have good comprehensive properties, but they are generally more expensive than traditional plastic films, which makes them extremely difficult to promote and use.
  • starch-based biodegradable films are very competitive, and starch is 100% bio-based, green and renewable.
  • the invention patent application with the publication number CN103435981A selects starch and PBAT as the substrate to prepare a fully degradable film with a biobased content of up to 30%.
  • the film has good toughness and the elongation at break is up to 271%.
  • due to the low tensile strength it is less than 3 MPa, which is difficult to meet the requirements for use.
  • the fully biodegradable material polyglycolide (PGA) has greater mechanical strength and its tensile strength exceeds 100. MPa, and the price is lower than other biodegradable materials, so PGA, starch and PBAT are highly compounded, and it is expected to produce a low-cost bio-based fully degradable film with excellent comprehensive performance.
  • the invention aims at the problem that the existing biodegradable film has high cost and is difficult to be popularized and applied, and provides a low-cost bio-based fully degradable film and a preparation method thereof.
  • the invention uses PGA, starch and PBAT as a substrate to reduce the melting temperature of PGA by plasticizing modification, so as to avoid serious gelatinization of starch during high temperature blending; and use reactive auxiliaries to solve PGA, PBAT and thermoplastic starch. (TPS) interface compatibility problem, through the blending modification technology to prepare a low-cost bio-based fully degradable film special materials.
  • TPS thermoplastic starch
  • a low-cost bio-based fully degradable film consisting of the following mass parts of raw materials: 15 ⁇ 25 parts of polyglycolide, 25 ⁇ 35 parts of corn starch, and polybutylene adipate/butylene terephthalate 35 ⁇ 55 Parts, starch plasticizer 3.75 ⁇ 12.25 parts, compatibilizer 5 parts, citric acid 0.5 ⁇ 0.7 parts, acetyl tributyl citrate 0.75 ⁇ 1.25 parts, maleic anhydride 0.3 ⁇ 0.5 parts, antioxidant 164 0.2 parts, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole 0.2 part.
  • starch plasticizer is one or two of glycerin, ethylene glycol, formamide, urea, and ethylenediamine.
  • the compatibilizing agent is any one of ethylene butyl acrylate grafted glycidyl methacrylate, ethylene-acrylic acid copolymer, and ethylene-vinyl acetate copolymer.
  • the low cost bio-based fully degradable film provided by the present invention is prepared by the following steps:
  • the modified masterbatch prepared in the step (1) is added to the thermoplastic starch prepared in the step (2), and is mixed by a high-mixing machine and stirred at a low speed to prepare a mixed master batch;
  • step (3) (4) adding the mixed masterbatch prepared in the step (3) to a parallel twin-screw extruder, melt blending and air-cooling the pellets to prepare a bio-based low-cost fully degradable blown film material;
  • the blown film obtained in the step (4) is blown by a common high-pressure PE blown film machine to obtain a low-cost bio-based fully degradable film having a thickness of 15 ⁇ m and a width of 920 mm.
  • the temperature of the zone 1-7 of the twin-screw extruder described in the step (1) is 160 ° C, 180 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, and the head temperature is 220 ° C.
  • the high-mixer described in the step (2) has a heating temperature of 100 ° C, a rotation speed of 500 rpm, and a mixing time of 10 min.
  • the high-mixer described in the step (3) has a heating temperature of 100 ° C, a rotation speed of 200 rpm, and a mixing time of 4 minutes.
  • the temperature of the zone 1-7 of the twin-screw extruder described in the step (4) is 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, and the head temperature is 170 ° C.
  • the temperature of the ordinary high-pressure PE film blowing machine described in the step (5) is 150 ° C, 180 ° C, 180 ° C, and 180 ° C, respectively.
  • the low-cost bio-based fully degradable film provided by the invention has a bio-based content of more than 30%, a lower cost, and a tensile strength exceeding that of a conventional PE film, and solves the problem of “white pollution” and promotes the whole.
  • the promotion and application of biodegradable materials is of great significance.
  • the low-cost bio-based fully degradable film material is composed of the following mass parts of raw materials: 15 parts of polyglycolide, 25 parts of corn starch, 55 parts of polybutylene adipate/butylene terephthalate, 1.25 parts of glycerin, 2.5 parts of ethylene glycol, ethylene butyl acrylate grafted 5 parts of glycidyl methacrylate, 0.5 parts of citric acid, 0.75 parts of acetyl tributyl citrate, 0.3 parts of maleic anhydride, 0.2 parts of antioxidant 164, 2- (2'-Hydroxy-5'-methylphenyl)benzotriazole 0.2 part.
  • the polyglycolide, maleic anhydride and acetyl tributyl citrate were uniformly mixed and then added to a parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 was set to 160 ° C in this order.
  • the temperature of the extruder 1-7 was set to 160 ° C in this order. 180 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, the head temperature is 220 ° C, the preparation of plasticized end-capped PGA modified material;
  • corn starch, glycerin and ethylene glycol are added to a high-mixer, and the heating temperature of the high-mixer is set to 100 ° C, the rotation speed is 500 rpm, and the mixing time is 10 min to prepare a thermoplastic starch;
  • PGA plasticized end-capped modified material polyadipate/butylene terephthalate, ethylene butyl acrylate grafted glycidyl methacrylate, citric acid, antioxidant 164 and 2-(2'- Hydroxy-5'-methylphenyl)benzotriazole was added to the prepared thermoplastic starch, and the mixing temperature of the high mixer was set to 100 ° C, the rotation speed was 200 rpm, and the mixing time was 4 min. Masterbatch
  • the mixed masterbatch is added to the parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 zone is set to 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, At 180 ° C, the head temperature is 170 ° C, and a bio-based low-cost fully degradable blown film material is prepared;
  • the prepared bio-based low-cost fully degradable blown film is blown by a common PE blown film machine, and the temperature of the blown film machine 1-4 is 150 ° C, 180 ° C, 180 ° C, 180 ° C, respectively.
  • the film thickness was 15 ⁇ m and the width was 920 mm.
  • the low-cost bio-based fully degradable film material consists of the following mass parts of raw materials: 20 parts of polyglycolide, 30 parts of corn starch, 45 parts of polybutylene adipate / butylene terephthalate, 4 parts of formamide, urea 2 parts, ethylene butyl acrylate grafted 5 parts of glycidyl methacrylate, 0.6 parts of citric acid, 1 part of acetyl tributyl citrate, 0.4 parts of maleic anhydride, 0.2 parts of antioxidant 164, 2-(2' -Hydroxy-5'-methylphenyl)benzotriazole 0.2 part.
  • the polyglycolide, maleic anhydride and acetyl tributyl citrate were uniformly mixed and then added to a parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 was set to 160 ° C in this order.
  • the temperature of the extruder 1-7 was set to 160 ° C in this order. 180 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, the head temperature is 220 ° C, the preparation of plasticized end-capped PGA modified material;
  • corn starch, formamide and urea are added to a high-mixer, and the heating temperature of the high-mixer is set to 100 ° C, the rotation speed is 500 rpm, and the mixing time is 10 min to prepare a thermoplastic starch;
  • PGA plasticized end-capped modified material polyadipate/butylene terephthalate, ethylene butyl acrylate grafted glycidyl methacrylate, citric acid, antioxidant 164 and 2-(2'- Hydroxy-5'-methylphenyl)benzotriazole was added to the prepared thermoplastic starch, and the mixing temperature of the high mixer was set to 100 ° C, the rotation speed was 200 rpm, and the mixing time was 4 min. Masterbatch
  • the mixed masterbatch is added to the parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 zone is set to 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, At 180 ° C, the head temperature is 170 ° C, and a bio-based low-cost fully degradable blown film material is prepared;
  • the prepared bio-based low-cost fully degradable blown film is blown by a common PE blown film machine, and the temperature of the blown film machine 1-4 is 150 ° C, 180 ° C, 180 ° C, 180 ° C, respectively.
  • the film thickness was 15 ⁇ m and the width was 920 mm.
  • the low-cost bio-based fully degradable film material consists of the following parts by mass of raw materials: 25 parts of polyglycolide, 35 parts of corn starch, 35 parts of polybutylene adipate/butylene terephthalate, and ethylenediamine 12.25 parts, ethylene butyl acrylate grafted 5 parts of glycidyl methacrylate, 0.7 parts of citric acid, 1.25 parts of acetyl tributyl citrate, 0.5 parts of maleic anhydride, 0.2 parts of antioxidant 164, 2-(2' -Hydroxy-5'-methylphenyl)benzotriazole 0.2 part.
  • the polyglycolide, maleic anhydride and acetyl tributyl citrate were uniformly mixed and then added to a parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 was set to 160 ° C in this order.
  • the temperature of the extruder 1-7 was set to 160 ° C in this order. 180 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, the head temperature is 220 ° C, the preparation of plasticized end-capped PGA modified material;
  • the corn starch and the ethylenediamine dimethylamide are added to the high-mixer, and the heating temperature of the high-mixer is set to 100 ° C, the rotation speed is 500 rpm, and the mixing time is 10 min to prepare a thermoplastic starch;
  • PGA plasticized end-capped modified material polyadipate/butylene terephthalate, ethylene butyl acrylate grafted glycidyl methacrylate, citric acid, antioxidant 164 and 2-(2'- Hydroxy-5'-methylphenyl)benzotriazole was added to the prepared thermoplastic starch, and the mixing temperature of the high mixer was set to 100 ° C, the rotation speed was 200 rpm, and the mixing time was 4 min. Masterbatch
  • the mixed masterbatch is added to the parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 zone is set to 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, At 180 ° C, the head temperature is 170 ° C, and a bio-based low-cost fully degradable blown film material is prepared;
  • the prepared bio-based low-cost fully degradable blown film is blown by a common PE blown film machine, and the temperature of the blown film machine 1-4 is 150 ° C, 180 ° C, 180 ° C, 180 ° C, respectively.
  • the film thickness was 15 ⁇ m and the width was 920 mm.
  • the low-cost bio-based fully degradable film material consists of the following parts by mass of raw materials: 25 parts of polyglycolide, 35 parts of corn starch, 35 parts of polybutylene adipate/butylene terephthalate, and ethylenediamine 12.25 parts, 5 parts of ethylene-acrylic acid copolymer, 0.7 parts of citric acid, 1.25 parts of acetyl tributyl citrate, 0.5 parts of maleic anhydride, 0.2 parts of antioxidant 164, 2-(2'-hydroxy-5'-A Phenyl phenyl) benzotriazole 0.2 parts.
  • the polyglycolide, maleic anhydride and acetyl tributyl citrate were uniformly mixed and then added to a parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 was set to 160 ° C in this order.
  • the temperature of the extruder 1-7 was set to 160 ° C in this order. 180 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, the head temperature is 220 ° C, the preparation of plasticized end-capped PGA modified material;
  • the corn starch and the ethylenediamine dimethylamide are added to the high-mixer, and the heating temperature of the high-mixer is set to 100 ° C, the rotation speed is 500 rpm, and the mixing time is 10 min to prepare a thermoplastic starch;
  • PGA plasticized end-capped modified material polyadipate/butylene terephthalate, ethylene-acrylic acid copolymer, citric acid, antioxidant 164 and 2-(2'-hydroxy-5'-methyl Phenyl)benzotriazole was added to the prepared thermoplastic starch, and the mixing temperature of the high mixer was set to 100 ° C, the rotation speed was 200 rpm, and the mixing time was 4 min to prepare a mixed master batch;
  • the mixed masterbatch is added to the parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 zone is set to 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, At 180 ° C, the head temperature is 170 ° C, and a bio-based low-cost fully degradable blown film material is prepared;
  • the prepared bio-based low-cost fully degradable blown film is blown by a common PE blown film machine, and the temperature of the blown film machine 1-4 is 150 ° C, 180 ° C, 180 ° C, 180 ° C, respectively.
  • the film thickness was 15 ⁇ m and the width was 920 mm.
  • the low-cost bio-based fully degradable film material consists of the following parts by mass of raw materials: 25 parts of polyglycolide, 35 parts of corn starch, 35 parts of polybutylene adipate/butylene terephthalate, and ethylenediamine 12.25 parts, 5 parts of ethylene-vinyl acetate copolymer, 0.7 parts of citric acid, 1.25 parts of acetyl tributyl citrate, 0.5 parts of maleic anhydride, 0.2 parts of antioxidant 164, 2-(2'-hydroxy-5'- Methylphenyl) benzotriazole 0.2 parts.
  • the polyglycolide, maleic anhydride and acetyl tributyl citrate were uniformly mixed and then added to a parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 was set to 160 ° C in this order.
  • the temperature of the extruder 1-7 was set to 160 ° C in this order. 180 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, 230 ° C, the head temperature is 220 ° C, the preparation of plasticized end-capped PGA modified material;
  • the corn starch and the ethylenediamine dimethylamide are added to the high-mixer, and the heating temperature of the high-mixer is set to 100 ° C, the rotation speed is 500 rpm, and the mixing time is 10 min to prepare a thermoplastic starch;
  • PGA plasticized end-capped modified material polyadipate/butylene terephthalate, ethylene-vinyl acetate copolymer, citric acid, antioxidant 164 and 2-(2'-hydroxy-5'-A Benzyl)benzotriazole was added to the prepared thermoplastic starch, and the mixing temperature of the high mixer was set to 100 ° C, the rotation speed was 200 rpm, and the mixing time was 4 min to prepare a mixed master batch;
  • the mixed masterbatch is added to the parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 zone is set to 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, At 180 ° C, the head temperature is 170 ° C, and a bio-based low-cost fully degradable blown film material is prepared;
  • the prepared bio-based low-cost fully degradable blown film is blown by a common PE blown film machine, and the temperature of the blown film machine 1-4 is 150 ° C, 180 ° C, 180 ° C, 180 ° C, respectively.
  • the film thickness was 15 ⁇ m and the width was 920 mm.
  • the fully biodegradable film material consists of the following parts by mass of raw materials: 25 parts of corn starch, 75 parts of polybutylene adipate/butylene terephthalate, 1.25 parts of glycerol, 2.5 parts of ethylene glycol, and butyl acrylate. 5 parts of glycidyl methacrylate, 0.5 parts of citric acid, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole were added.
  • thermoplastic starch corn starch, glycerol and ethylene glycol were added to a high-mixer, and the heating temperature of the high-mixer was set to 100 ° C, the rotation speed was 500 rpm, and the mixing time was 10 min to prepare a thermoplastic starch;
  • polyadipate/butylene terephthalate, ethylene butyl acrylate grafted glycidyl methacrylate, citric acid, antioxidant 164 and 2-(2'-hydroxy-5'-methylbenzene Benzotriazole was added to the prepared thermoplastic starch, and the mixing temperature of the high mixer was set to 100 ° C, the rotation speed was 200 rpm, and the mixing time was 4 min to prepare a mixed master batch;
  • the mixed masterbatch is added to the parallel co-rotating twin-screw extruder for blending and extrusion, and the temperature of the extruder 1-7 zone is set to 150 ° C, 170 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, 180 ° C, the head temperature is 170 ° C, the preparation of a fully biodegradable blown film material;
  • the prepared biodegradable blown film material is blown through a common PE blown film machine, and the temperature of the film blowing machine 1-4 is 150 ° C, 180 ° C, 180 ° C, 180 ° C, respectively.
  • the film thickness was 15 ⁇ m and the width was 920 mm.
  • LG FB 3000 Low-density polyethylene
  • This example is intended to evaluate the mechanical properties of the films prepared in Examples 1 to 5 and Comparative Examples 1, 2, and the relevant tests are in accordance with GB/T 1040.3-2006 in a universal tensile testing machine (CMT-4304, Shenzhen Xinsisi). Co., Ltd.), the test rate is 50mm / min, the test results are shown in Table 1.
  • test data of Examples 1 to 3 it can be seen from the test data of Examples 1 to 3 that as the PGA content in the formulation system increases, the tensile strength of the film increases and the elongation at break gradually decreases; the test data of Examples 3 to 5 can be used. It can be seen that ethylene butyl acrylate grafted glycidyl methacrylate in three compatibilizers has the best compatibilizing effect on PGA, TPS and PBAT three phases; from Examples 1 to 5 and Comparative Examples 1 to 2 The test data shows that the low-cost bio-based fully degradable film provided by the present invention has greater tensile strength than the bio-based fully degradable film without PGA and the conventional PE film.
  • the invention uses PGA, starch and PBAT as the substrate, and reduces the melting temperature of PGA by plasticizing modification, thereby avoiding the serious gelatinization of starch when blending at high temperature; using reactive additives to solve the problem
  • the interfacial compatibility between PGA, PBAT and thermoplastic starch (TPS) was solved.
  • the low-cost bio-based fully degradable film was prepared by blending modification technology.
  • the low-cost bio-based fully degradable film provided by the invention has a bio-based content of more than 30%, a lower cost, and a tensile strength exceeding that of a conventional PE film, and solves the problem of “white pollution” and promotes the promotion of the whole biodegradable material. Application is very important.
  • the PGA used in the present invention is produced by our company, and other raw materials such as PBAT, maleic anhydride, corn starch, starch plasticizer, compatibilizer, citric acid, acetyl tributyl citrate, antioxidant 164, 2-(2) '-Hydroxy-5'-methylphenyl)benzotriazole can be purchased directly from the market.
  • PBAT maleic anhydride
  • corn starch corn starch
  • starch plasticizer compatibilizer
  • citric acid acetyl tributyl citrate
  • antioxidant 164 2-(2) '-Hydroxy-5'-methylphenyl)benzotriazole

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Abstract

本发明公开了一种低成本生物基全降解薄膜及其制备方法，所述薄膜各组分按质量份数计的配比是：聚乙交酯15~25份、玉米淀粉25~35份、聚己二酸/对苯二甲酸丁二酯35~55份、相容剂5份、淀粉增塑剂3.75~12.25份、柠檬酸0.5~0.7份、乙酰柠檬酸三丁酯0.75~1.25份、马来酸酐0.3~0.5份、抗氧剂164 0.2份、2-(2'-羟基-5'-甲基苯基)苯并三氮唑0.2份。本发明提供的低成本生物基全降解薄膜生物基含量可达30%以上，成本较低，拉伸强度超过传统PE薄膜，对于解决"白色污染"问题、促进全生物降解材料的推广与应用具有十分重要的意义。

Description

低成本生物基全降解薄膜及其制备方法 技术领域
本发明属于全生物降解材料技术领域，涉及一种生物降解薄膜，更具体的说是涉及一种低成本生物基全降解薄膜及其制备方法。
 背景技术
塑料包装膜的使用给我们的生产和生活带来了极大的便利。但因为传统的塑料包装膜均由不可降解的石油基材料制备而成，其大量使用不仅造成了资源浪费，还给环境带来了“白色污染”，从而引发了社会的广泛关注。废弃塑料膜的焚烧和就地掩埋会造成严重的大气污染和土壤污染，而二次回收又存在着回收率低、材料性能劣化和回收成本过高等缺点，因此，推广使用全生物降解材料无疑是从根本上解决“白色污染”这一问题的有效途径。
目前，我国对于全生物降解薄膜的研发已取得了显著成果，例如申请公布号为CN102702696A的发明专利以聚乳酸（PLA）和聚己二酸/对苯二甲酸丁二酯（PBAT）为主基材，制备的全生物降解薄膜吹塑厚度可达20μm，拉伸强度为11~12.1MPa，断裂伸长率超过150%；申请公布号为CN103589124A的发明专利同样制备了一种PLA/PBAT全生物降解薄膜，并通过添加复合增溶剂和矿物填料的方式使所制薄膜的拉伸强度最高可达61 MPa；申请公布号为CN102675839A的发明专利以PLA、PBAT和聚碳酸亚丙酯（PPC）为基材，所制全生物降解薄膜的落镖冲击强度超过传统的聚乙烯薄膜。以上全生物降解薄膜都有着不错的综合性能，但与传统塑料薄膜相比普遍存在着价格昂贵的缺点，从而使得其推广使用遭遇了极大的障碍。
在众多的全生物降解薄膜中，淀粉基全生物降解薄膜极具价格优势，且淀粉是100%生物基材料，绿色环保且可再生。申请公布号为CN103435981A的发明专利申请选取淀粉和PBAT为基材，制备出一种生物基含量高达30%的全降解薄膜。该薄膜具有良好的韧性，断裂伸长率最高可达271%，但由于拉伸强度较低，不足3 MPa，难以满足使用要求。而全生物降解材料聚乙交酯（PGA）具有较大的力学强度，其拉伸强度超过100 MPa，且与其他全生物降解材料相比价格较低，因此将PGA、淀粉和PBAT高效复合，有望制备出综合性能优良的低成本生物基全降解薄膜。
 技术问题
本发明针对现有全生物降解薄膜成本较高，难以推广应用的问题，提供了一种低成本生物基全降解薄膜及其制备方法。本发明以PGA、淀粉和PBAT为基材，通过增塑改性降低PGA的熔融温度，以避免淀粉在高温共混时的严重糊化；选用反应性助剂以突破解决PGA、PBAT和热塑性淀粉（TPS）间的界面相容性问题，通过共混改性技术制备出低成本生物基全降解薄膜专用料。
 技术解决方案
在此处键入技术解决方案描述段落。为了达到上述目的，本发明采用如下技术方案。
一种低成本生物基全降解薄膜，由以下质量份数的原料组成：聚乙交酯15~25份、玉米淀粉25~35份、聚己二酸/对苯二甲酸丁二酯35~55份、淀粉增塑剂3.75~12.25份、相容剂5份、柠檬酸0.5~0.7份、乙酰柠檬酸三丁酯0.75~1.25份、马来酸酐0.3~0.5份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
进一步，所述的淀粉增塑剂为丙三醇、乙二醇、甲酰胺、尿素、乙二撑二甲酰胺中的一种或两种。
进一步，所述的相容剂为乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯、乙烯-丙烯酸共聚物、和乙烯-醋酸乙烯共聚物的任意一种。
本发明提供的低成本生物基全降解薄膜通过以下步骤进行制备：
（1）将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯加入平行双螺杆挤出机中，熔融共混并风冷切粒，制备出增塑且封端改性的聚乙交酯母粒；
（2）将玉米淀粉和淀粉增塑剂加入到高混机中，加热并高速搅拌，制备成热塑性淀粉；
（3）将聚己二酸/对苯二甲酸丁二酯、相容剂、柠檬酸、抗氧剂164、2-(2’-羟基-5’-甲基苯基)苯并三氮唑和步骤（1）制备的改性母粒一起加入步骤（2）制备的热塑性淀粉中，通过高混机加热低速搅拌均匀后制备成混合母料；
（4）将步骤（3）制备的混合母料加入平行双螺杆挤出机中，熔融共混并风冷切粒，制备出生物基低成本全降解吹膜料；
（5）将步骤（4）制得的吹膜料采用普通高压PE吹膜机吹膜成型，得到厚度为15 μm，幅宽为920 mm的低成本生物基全降解薄膜。
进一步，步骤（1）所述的双螺杆挤出机1-7区的温度分别为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃。
进一步，步骤（2）所述的高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min。
进一步，步骤（3）所述的高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min。
进一步，步骤（4）所述的双螺杆挤出机1-7区的温度分别为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃。
进一步，步骤（5）所述的普通高压PE吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
 有益效果
与现有技术相比，本发明提供的低成本生物基全降解薄膜的生物基含量可达30%以上，成本较低，拉伸强度超过传统PE薄膜，对于解决“白色污染”问题、促进全生物降解材料的推广与应用具有十分重要的意义。
本发明的具体实施方式
以下通过实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。
若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
实施例1:
低成本生物基全降解薄膜料由以下质量份数的原料组成：聚乙交酯15份、玉米淀粉25份、聚己二酸/对苯二甲酸丁二酯55份、丙三醇1.25份、乙二醇2.5份、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯5份、柠檬酸0.5份、乙酰柠檬酸三丁酯0.75份、马来酸酐0.3份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
低成本生物基全降解薄膜的制备：
首先将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯混合均匀后加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃，制备增塑封端的PGA改性料；
然后将玉米淀粉、丙三醇和乙二醇加入到高混机中，设定高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min，制备成热塑性淀粉；
接着将PGA增塑封端改性料、聚己二酸/对苯二甲酸丁二酯、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯、柠檬酸、抗氧剂164和2-(2’-羟基-5’-甲基苯基)苯并三氮唑加入到制备的热塑性淀粉中，设定高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min，制备成混合母料；
再将混合母料加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃，制备出生物基低成本全降解吹膜料；
最后将制备的生物基低成本全降解吹膜料通过普通PE吹膜机吹膜，吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
所制薄膜厚度为15 μm，幅宽为920 mm。
实施例2:
低成本生物基全降解薄膜料由以下质量份数的原料组成：聚乙交酯20份、玉米淀粉30份、聚己二酸/对苯二甲酸丁二酯45份、甲酰胺4份、尿素2份、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯5份、柠檬酸0.6份、乙酰柠檬酸三丁酯1份、马来酸酐0.4份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
低成本生物基全降解薄膜的制备：
首先将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯混合均匀后加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃，制备增塑封端的PGA改性料；
然后将玉米淀粉、甲酰胺和尿素加入到高混机中，设定高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min，制备成热塑性淀粉；
接着将PGA增塑封端改性料、聚己二酸/对苯二甲酸丁二酯、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯、柠檬酸、抗氧剂164和2-(2’-羟基-5’-甲基苯基)苯并三氮唑加入到制备的热塑性淀粉中，设定高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min，制备成混合母料；
再将混合母料加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃，制备出生物基低成本全降解吹膜料；
最后将制备的生物基低成本全降解吹膜料通过普通PE吹膜机吹膜，吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
所制薄膜厚度为15 μm，幅宽为920 mm。
实施例3:
低成本生物基全降解薄膜料由以下质量份数的原料组成：聚乙交酯25份、玉米淀粉35份、聚己二酸/对苯二甲酸丁二酯35份、乙二撑二甲酰胺12.25份、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯5份、柠檬酸0.7份、乙酰柠檬酸三丁酯1.25份、马来酸酐0.5份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
低成本生物基全降解薄膜的制备：
首先将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯混合均匀后加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃，制备增塑封端的PGA改性料；
然后将玉米淀粉和乙二撑二甲酰胺加入到高混机中，设定高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min，制备成热塑性淀粉；
接着将PGA增塑封端改性料、聚己二酸/对苯二甲酸丁二酯、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯、柠檬酸、抗氧剂164和2-(2’-羟基-5’-甲基苯基)苯并三氮唑加入到制备的热塑性淀粉中，设定高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min，制备成混合母料；
再将混合母料加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃，制备出生物基低成本全降解吹膜料；
最后将制备的生物基低成本全降解吹膜料通过普通PE吹膜机吹膜，吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
所制薄膜厚度为15 μm，幅宽为920 mm。
实施例4：
低成本生物基全降解薄膜料由以下质量份数的原料组成：聚乙交酯25份、玉米淀粉35份、聚己二酸/对苯二甲酸丁二酯35份、乙二撑二甲酰胺12.25份、乙烯-丙烯酸共聚物5份、柠檬酸0.7份、乙酰柠檬酸三丁酯1.25份、马来酸酐0.5份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
低成本生物基全降解薄膜的制备：
首先将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯混合均匀后加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃，制备增塑封端的PGA改性料；
然后将玉米淀粉和乙二撑二甲酰胺加入到高混机中，设定高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min，制备成热塑性淀粉；
接着将PGA增塑封端改性料、聚己二酸/对苯二甲酸丁二酯、乙烯-丙烯酸共聚物、柠檬酸、抗氧剂164和2-(2’-羟基-5’-甲基苯基)苯并三氮唑加入到制备的热塑性淀粉中，设定高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min，制备成混合母料；
再将混合母料加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃，制备出生物基低成本全降解吹膜料；
最后将制备的生物基低成本全降解吹膜料通过普通PE吹膜机吹膜，吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
所制薄膜厚度为15 μm，幅宽为920 mm。
实施例5：
低成本生物基全降解薄膜料由以下质量份数的原料组成：聚乙交酯25份、玉米淀粉35份、聚己二酸/对苯二甲酸丁二酯35份、乙二撑二甲酰胺12.25份、乙烯-醋酸乙烯共聚物5份、柠檬酸0.7份、乙酰柠檬酸三丁酯1.25份、马来酸酐0.5份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
低成本生物基全降解薄膜的制备：
首先将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯混合均匀后加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃，制备增塑封端的PGA改性料；
然后将玉米淀粉和乙二撑二甲酰胺加入到高混机中，设定高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min，制备成热塑性淀粉；
接着将PGA增塑封端改性料、聚己二酸/对苯二甲酸丁二酯、乙烯-醋酸乙烯共聚物、柠檬酸、抗氧剂164和2-(2’-羟基-5’-甲基苯基)苯并三氮唑加入到制备的热塑性淀粉中，设定高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min，制备成混合母料；
再将混合母料加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃，制备出生物基低成本全降解吹膜料；
最后将制备的生物基低成本全降解吹膜料通过普通PE吹膜机吹膜，吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
所制薄膜厚度为15 μm，幅宽为920 mm。
对比例1：
全生物降解薄膜料由以下质量份数的原料组成：玉米淀粉25份、聚己二酸/对苯二甲酸丁二酯75份、丙三醇1.25份、乙二醇2.5份、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯5份、柠檬酸0.5份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
全生物降解薄膜的制备：
首先将玉米淀粉、丙三醇和乙二醇加入到高混机中，设定高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min，制备成热塑性淀粉；
然后将聚己二酸/对苯二甲酸丁二酯、乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯、柠檬酸、抗氧剂164和2-(2’-羟基-5’-甲基苯基)苯并三氮唑加入到制备的热塑性淀粉中，设定高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min，制备成混合母料；
再将混合母料加入到平行同向双螺杆挤出机中共混挤出，设定挤出机1-7区温度依次为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃，制备出全生物降解吹膜料；
最后将制备的全生物降解吹膜料通过普通PE吹膜机吹膜，吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
所制薄膜厚度为15 μm，幅宽为920 mm。
对比例2：
将低密度聚乙烯(LG公司FB 3000)通过普通PE吹膜机吹膜，吹膜机各区温度均为145℃。所制薄膜厚度为15μm，幅宽为920 mm。
实施例6：
本实施例旨在对实施例1~5和对比例1、2所制薄膜的力学性能进行评价，相关检测依照GB/T1040.3-2006在万能拉伸试验机（CMT-4304，深圳新三思有限公司）上进行，试验速率为50mm/min，检测结果详见表一。
表一  不同薄膜的力学性能
Figure 652065dest_path_image001
由实施例1~3的检测数据可以看出，随着配方体系中PGA含量的增加，薄膜的拉伸强度不断增大，断裂伸长率逐渐减小；由实施例3~5的检测数据可以看出，在三种相容剂中乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯对于PGA、TPS和PBAT三相的增容效果最佳；由实施例1~5和对比例1~2的检测数据可以看出，与未添加PGA的生物基全降解薄膜以及传统的PE薄膜相比，本发明提供的低成本生物基全降解薄膜具有更大的拉伸强度。
综上所述，本发明以PGA、淀粉和PBAT为基材，通过增塑改性降低了PGA的熔融温度，避免了淀粉在高温共混时的严重糊化；选用反应性助剂以突破解决了PGA、PBAT和热塑性淀粉（TPS）间的界面相容性问题，通过共混改性技术制备出了低成本生物基全降解薄膜专用料。而且，本发明提供的低成本生物基全降解薄膜生物基含量可达30%以上，成本较低，拉伸强度超过传统PE薄膜，对于解决“白色污染”问题、促进全生物降解材料的推广与应用具有十分重要的意义。
本发明所用PGA为我公司自己生产，其他原料如PBAT、马来酸酐、玉米淀粉、淀粉增塑剂、相容剂、柠檬酸 、乙酰柠檬酸三丁酯、抗氧剂164、2-(2’-羟基-5’-甲基苯基)苯并三氮唑等可从市场直接采购。
上述描述仅是对本发明较佳实施例的描述，并非是对本发明范围的任何限定。任何熟悉该领域的普通技术人员根据上述揭示的技术内容做出的任何变更或修饰均应当视为等同的有效实施例，均属于本发明技术方案保护的范围。

Claims (9)

  1. 一种低成本生物基全降解薄膜，其特征在于，由以下质量份数的原料组成：聚乙交酯15~25份、玉米淀粉25~35份、聚己二酸/对苯二甲酸丁二酯35~55份、淀粉增塑剂3.75~12.25份、相容剂5份、柠檬酸0.5~0.7份、乙酰柠檬酸三丁酯0.75~1.25份、马来酸酐0.3~0.5份、抗氧剂164 0.2份、2-(2’-羟基-5’-甲基苯基)苯并三氮唑0.2份。
  2. 根据权利要求1所述的低成本生物基全降解薄膜，其特征在于：所述的淀粉增塑剂为丙三醇、乙二醇、甲酰胺、尿素、乙二撑二甲酰胺中的任意一种或两种。
  3. 根据权利要求1所述的低成本生物基全降解薄膜，其特征在于：所述的相容剂为乙烯丙烯酸丁酯接枝甲基丙烯酸缩水甘油酯、乙烯-丙烯酸共聚物、和乙烯-醋酸乙烯共聚物的任意一种。
  4. 一种权利要求1所述的低成本生物基全降解薄膜的制备方法，其特征在于：包括如下步骤：
    （1）将聚乙交酯、马来酸酐和乙酰柠檬酸三丁酯加入平行双螺杆挤出机中，熔融共混并风冷切粒，制备出增塑且封端改性的聚乙交酯母粒；
    （2）将玉米淀粉和淀粉增塑剂加入到高混机中，加热并高速搅拌，制备成热塑性淀粉；
    （3）将聚己二酸/对苯二甲酸丁二酯、相容剂、柠檬酸、抗氧剂164、2-(2’-羟基-5’-甲基苯基)苯并三氮唑和步骤（1）制备的改性母粒一起加入步骤（2）制备的热塑性淀粉中，通过高混机加热低速搅拌均匀后制备成混合母料；
    （4）将步骤（3）制备的混合母料加入平行双螺杆挤出机中，熔融共混并风冷切粒，制备出生物基低成本全降解吹膜料；
    （5）将步骤（4）制得的吹膜料采用普通高压PE吹膜机吹膜成型，得到厚度为15 μm，幅宽为920 mm的低成本生物基全降解薄膜。
  5. 根据权利要求4所述的低成本生物基全降解薄膜的制备方法，其特征在于：步骤（1）所述的双螺杆挤出机1-7区的温度分别为160℃，180℃，230℃，230℃，230℃，230℃，230℃，机头温度为220℃。
  6. 根据权利要求4所述的低成本生物基全降解薄膜的制备方法，其特征在于：步骤（2）所述的高混机的加热温度为100 ℃，转速为500 rpm，混料时间为10 min。
  7. 根据权利要求4所述的低成本生物基全降解薄膜的制备方法，其特征在于：步骤（3）所述的高混机的加热温度为100 ℃，转速为200 rpm，混料时间为4 min。
  8. 根据权利要求4所述的低成本生物基全降解薄膜的制备方法，其特征在于：步骤（4）所述的双螺杆挤出机1-7区的温度分别为150℃，170℃，180℃，180℃，180℃，180℃，180℃，机头温度为170℃。
  9. 根据权利要求4所述的低成本生物基全降解薄膜的制备方法，其特征在于：步骤（5）所述的普通高压PE吹膜机1-4区的温度分别为150℃，180℃，180℃，180℃。
     
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