WO2022027602A1 - 多层可生物降解薄膜及其制备方法 - Google Patents

多层可生物降解薄膜及其制备方法 Download PDF

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WO2022027602A1
WO2022027602A1 PCT/CN2020/107846 CN2020107846W WO2022027602A1 WO 2022027602 A1 WO2022027602 A1 WO 2022027602A1 CN 2020107846 W CN2020107846 W CN 2020107846W WO 2022027602 A1 WO2022027602 A1 WO 2022027602A1
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layer
parts
biodegradable film
starch
film
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PCT/CN2020/107846
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English (en)
French (fr)
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陈昌平
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南京五瑞生物降解新材料研究院有限公司
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Priority to AU2020227132A priority Critical patent/AU2020227132A1/en
Priority to PCT/CN2020/107846 priority patent/WO2022027602A1/zh
Publication of WO2022027602A1 publication Critical patent/WO2022027602A1/zh

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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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a multi-layer biodegradable film and a preparation method thereof, belonging to the field of biodegradable plastics.
  • Biodegradable resins are very important for buffering the impact of white pollution on the earth.
  • Polyvinyl alcohol (PVA) is a water-soluble polymer with water solubility and biodegradability, and is increasingly used in film packaging materials.
  • the mixture of PVA/starch has high cost performance and moderate
  • the mechanical strength of biodegradable materials is currently a research hotspot of biodegradable materials.
  • PVA/starch film has good water solubility and excellent gas barrier properties to oxygen and nitrogen, but due to the presence of a large number of hydroxyl groups in the side chain of PVA/starch, it has hygroscopicity and poor moisture resistance, resulting in limited use environment .
  • PBAT is a copolymer of butylene adipate and butylene terephthalate. It has both the characteristics of PBA and PBT, and has good ductility and elongation at break, as well as good heat resistance. and impact performance; in addition, it also has excellent biodegradability, which is very active in the research of biodegradable plastics and one of the best biodegradable materials in the market.
  • PHA Polyhydroxyalkanoates
  • the purpose of the present invention is to provide a multi-layer biodegradable film, which has both good air tightness and good waterproof effect.
  • a multi-layer biodegradable film which is composed of a surface layer, a core layer and an inner layer, is characterized in that: the composition ratio of the core layer is: 100 parts of PVA, 60-100 parts of starch, 30-42 parts of plasticizer, 0.4-1.0 part of chemical modifier, 0.2-0.6 part of chain extender; the composition ratio of the surface layer and the inner layer is: 100 parts of PBAT, 30-50 parts of PHA, and 1-3 parts of lubricant.
  • the starch is hydroxypropyl starch.
  • the plasticizer is glycerin or epoxidized soybean oil.
  • the chemical modifier is citric acid.
  • the lubricant is oleic acid amide.
  • the present invention also discloses a method for preparing the above-mentioned multilayer biodegradable film, the steps of which include:
  • plasticizer Add a part of plasticizer to PVA, stir at high speed, dry, add the rest of plasticizer, chemical modifier and chain extender to starch, stir at high speed, dry, and then send the two into the mixer for mixing sent to twin-screw extruder for granulation;
  • B. PBAT, PHA and lubricant are sent to the mixer for mixing and then sent to the twin-screw extruder for granulation;
  • the surface layer, core layer and inner layer masterbatch are made into biodegradable film by three-layer co-extrusion blow molding process.
  • the material extrusion speed of the three extruders is 0.5:1.5:0.5, and the processing temperature is 200 °C , the screw speed is 60rpm, and the film pulling speed is 45m/min.
  • a layer of film with good water barrier is attached inside and outside the PVA/starch film with good air tightness, and the obtained film has both good air tightness and water resistance, and can be Completely biodegradable and environmentally friendly, it is especially suitable for food packaging.
  • the multi-layer biodegradable film is composed of a surface layer, a core layer and an inner layer.
  • the composition ratio of the core layer is: 100 parts of PVA, 80 parts of hydroxypropyl starch, 40 parts of glycerin, 0.8 parts of citric acid, and isocyanates 0.5 part of chain agent; the component proportions of the surface layer and the inner layer are: 100 parts of PBAT, 40 parts of PHA, and 2 parts of lubricant oleic acid amide.
  • the multi-layer biodegradable film is composed of a surface layer, a core layer and an inner layer.
  • the composition ratio of the core layer is: 100 parts of PVA, 60 parts of hydroxypropyl starch, 30 parts of epoxidized soybean oil, 0.4 parts of citric acid, 0.2 part of isocyanate chain extender;
  • the composition ratio of the surface layer and the inner layer is: 100 parts of PBAT, 30 parts of PHA, and 1 part of lubricant oleic acid amide.
  • the multi-layer biodegradable film is composed of a surface layer, a core layer and an inner layer, and is characterized in that: the composition ratio of the core layer is: 100 parts of PVA, 100 parts of hydroxypropyl starch, 42 parts of glycerin, and 1.0 part of citric acid , 0.2-0.6 part of isocyanate chain extender; the composition ratio of the surface layer and the inner layer is: 100 parts of PBAT, 50 parts of PHA, and 3 parts of lubricant oleic acid amide.
  • the preparation method of the multi-layer biodegradable film in the embodiment 1-3, its steps include:
  • B. PBAT, PHA and lubricant are sent to the mixer for mixing and then sent to the twin-screw extruder for granulation;
  • the surface layer, core layer and inner layer masterbatch are made into biodegradable film by three-layer co-extrusion blow molding process.
  • the material extrusion speed of the three extruders is 0.5:1.5:0.5, and the processing temperature is 200 °C , the screw speed is 60rpm, the film pulling speed is 45m/min, and the film thickness is 0.03mm.
  • the prepared film has good air tightness and water resistance, and can be completely biodegraded, and is especially suitable for use as a food packaging bag.

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  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

本发明公开了一种多层可生物降解薄膜，由表层、芯层和里层组成，其特征在于：所述芯层的组分配比为：PVA100份、淀粉60-100份、增塑剂30-42份、化学改性剂0.4-1.0份、扩链剂0.2-0.6份；所述表层和里层的组分配比为：PBAT100份、PHA 30-50份、润滑剂1-3份。及其制备方法。本发明制得的多层可生物降解薄膜，在气密性良好的PVA/淀粉薄膜内外均附上一层具有良好隔水性的薄膜，所得薄膜兼具良好的气密性和防水性，且可完全生物降解，对环境友好，尤其适合用于食品包装。

Description

多层可生物降解薄膜及其制备方法 技术领域
本发明涉及一种多层可生物降解薄膜及其制备方法，属于可生物降解塑料领域。
背景技术
可生物降解树脂对于缓冲白色污染给地球造成的冲击有非常重要的意义。聚乙烯醇(PVA)是一种水溶性聚合物，具有可水溶解性和生物降解性，越来越多的被用于薄膜包装材料，其中PVA/淀粉的混合物由于具有较高的性价比和适中的机械强度，是目前可生物降解材料的研究热点。PVA/淀粉薄膜具有良好的水溶解性能，对氧气和氮气等具有优异的气体阻隔性，但由于PVA/淀粉侧链均存在大量羟基，因此具有吸湿性，防潮性极差，导致使用环境受限。
PBAT是己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物，兼具PBA和PBT的特性，既有较好的延展性和断裂伸长率，也有较好的耐热性和冲击性能；此外，还具有优良的生物降解性，是目前生物降解塑料研究中非常活跃和市场应用最好降解材料之一。
聚羟基脂肪酸酯(polyhydroxyalkanoates,PHA)，是很多微生物合成的一种细胞内聚酯，是一种天然的高分子生物降解材料。它具有很好的生物多样性，尤其是生物相容性，可用于PBAT的共混改性。
发明内容
本发明的目的在于提供一种多层可生物降解薄膜，既具有良好的气密性，又具有较好的防水效果。
本发明的目的通过以下技术方案实现：
一种多层可生物降解薄膜，由表层、芯层和里层组成，其特征在于：所述芯层的组分配比为：PVA100份、淀粉60-100份、增塑剂30-42份、化学改性剂0.4-1.0份、扩链剂0.2-0.6份；所述表层和里层的组分配比为：PBAT100份、PHA 30-50份、润滑剂1-3份。
优选的，所述淀粉为羟丙基淀粉。
优选的，所述增塑剂为甘油或环氧大豆油。
优选的，所述化学改性剂为柠檬酸。
优选的，所述润滑剂为油酸酰胺。
本发明还公开了上述的多层可生物降解薄膜的制备方法，其步骤包括：
A、在PVA中加入一部分增塑剂，高速搅拌，干燥，在淀粉中加入其余增塑剂和化学改性剂、扩链剂，高速搅拌，干燥，然后将两者送入混料机混合后送入双螺杆挤压机造粒；
B、将PBAT、PHA、润滑剂送入混料机混合后送入双螺杆挤压机造粒；
C、将表层、芯层和里层母粒采用三层共挤吹塑成型工艺制成可生物降解薄膜，三台挤出机的物料挤出速度为0.5：1.5：0.5，加工温度为200℃，螺杆转速为60rpm，薄膜牵引速度为45m/min。
优选的，步骤A中高速搅拌的速度为800rpm，时间为25分钟。
本发明制得的多层可生物降解薄膜，在气密性良好的PVA/淀粉薄膜内外均附上一层具有良好隔水性的薄膜，所得薄膜兼具良好的气密性和防水性，且可完全生物降解，对环境友好，尤其适合用于食品包装。
具体实施方式
本发明实施例中采用的材料为：
PVA1799D，上海石油化工有限公司；
成膜类PHA，北京蓝晶科技有限公司；
PBAT，BASF的Ecoflex；
羟丙基淀粉，河南恒瑞淀粉科技股份有限公司。
实施例1
本多层可生物降解薄膜，由表层、芯层和里层组成，所述芯层的组分配比为：PVA100份、羟丙基淀粉80份、甘油40份、柠檬酸0.8份、异氰酸酯类扩链剂0.5份；所述表层和里层的组分配比为：PBAT100份、PHA 40份、润滑剂油酸酰胺2份。
实施例2
本多层可生物降解薄膜，由表层、芯层和里层组成，所述芯层的组分配比为：PVA100份、羟丙基淀粉60份、环氧大豆油30份、柠檬酸0.4份、异氰酸酯类 扩链剂0.2份；所述表层和里层的组分配比为：PBAT100份、PHA 30份、润滑剂油酸酰胺1份。
实施例3
本多层可生物降解薄膜，由表层、芯层和里层组成，其特征在于：所述芯层的组分配比为：PVA100份、羟丙基淀粉100份、甘油42份、柠檬酸1.0份、异氰酸酯类扩链剂0.2-0.6份；所述表层和里层的组分配比为：PBAT100份、PHA50份、润滑剂油酸酰胺3份。
实施例1-3中的多层可生物降解薄膜的制备方法，其步骤包括：
A、在PVA中加入一半的增塑剂，高速搅拌，速度为800rpm，时间25分钟，干燥，在淀粉中加入其余增塑剂和化学改性剂、扩链剂，高速搅拌，速度为800rpm，时间25分钟，干燥，然后将两者送入混料机混合后送入双螺杆挤压机造粒；
B、将PBAT、PHA、润滑剂送入混料机混合后送入双螺杆挤压机造粒；
C、将表层、芯层和里层母粒采用三层共挤吹塑成型工艺制成可生物降解薄膜，三台挤出机的物料挤出速度为0.5：1.5：0.5，加工温度为200℃，螺杆转速为60rpm，薄膜牵引速度为45m/min，成膜厚度0.03mm。
制得的薄膜具有良好的气密性和防水性，且可完全生物降解，特别适合用做食品包装袋。

Claims (7)

  1. 一种多层可生物降解薄膜，由表层、芯层和里层组成，其特征在于：所述芯层的组分配比为：PVA 100份、淀粉60-100份、增塑剂30-42份、化学改性剂0.4-1.0份、扩链剂0.2-0.6份；所述表层和里层的组分配比为：PBAT 100份、PHA 30-50份、润滑剂1-3份。
  2. 根据权利要求1所述的多层可生物降解薄膜，其特征在于：所述淀粉为羟丙基淀粉。
  3. 根据权利要求2所述的多层可生物降解薄膜，其特征在于：所述增塑剂为甘油或环氧大豆油。
  4. 根据权利要求3所述的多层可生物降解薄膜，其特征在于：所述化学改性剂为柠檬酸。
  5. 根据权利要求4所述的多层可生物降解薄膜，其特征在于：所述润滑剂为油酸酰胺。
  6. 权利要求1-5中任一项所述的多层可生物降解薄膜的制备方法，其步骤包括：
    A、在PVA中加入一部分增塑剂，高速搅拌，干燥，在淀粉中加入其余增塑剂和化学改性剂、扩链剂，高速搅拌，干燥，然后将两者送入混料机混合后送入双螺杆挤压机造粒；
    B、将PBAT、PHA、润滑剂送入混料机混合后送入双螺杆挤压机造粒；
    C、将表层、芯层和里层母粒采用三层共挤吹塑成型工艺制成可生物降解薄膜，三台挤出机的物料挤出速度为0.5：1.5：0.5，加工温度为200℃，螺杆转速为60rpm，薄膜牵引速度为45m/min。
  7. 根据权利要求6所述的多层可生物降解薄膜的制备方法，其特征在于：步骤A中高速搅拌的速度为800rpm，时间为25分钟。
PCT/CN2020/107846 2020-08-07 2020-08-07 多层可生物降解薄膜及其制备方法 WO2022027602A1 (zh)

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CN116144147A (zh) * 2022-12-22 2023-05-23 四川大学 环境友好型复合材料及其制备方法

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CN115057107B (zh) * 2022-08-02 2023-07-04 山西农业大学 一种果蔬保鲜膜及其制备方法

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CN110626038A (zh) * 2019-09-27 2019-12-31 广东崇熙环保科技有限公司 生物降解膜及其制造方法
EP3636434A1 (en) * 2018-10-09 2020-04-15 Flexopack S.A. Thin film for waste packing

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EP3636434A1 (en) * 2018-10-09 2020-04-15 Flexopack S.A. Thin film for waste packing
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Publication number Priority date Publication date Assignee Title
CN114851672A (zh) * 2022-07-07 2022-08-05 山东兰德英科新材料科技有限公司 采用可生物降解输液袋专用料制备输液袋的方法
CN114851672B (zh) * 2022-07-07 2022-09-02 山东兰德英科新材料科技有限公司 采用可生物降解输液袋专用料制备输液袋的方法
CN116144147A (zh) * 2022-12-22 2023-05-23 四川大学 环境友好型复合材料及其制备方法
CN116144147B (zh) * 2022-12-22 2024-03-22 四川大学 环境友好型复合材料及其制备方法

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