WO2014032393A1 - Matériau entièrement biodégradable et son procédé de fabrication - Google Patents

Matériau entièrement biodégradable et son procédé de fabrication Download PDF

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Publication number
WO2014032393A1
WO2014032393A1 PCT/CN2013/000972 CN2013000972W WO2014032393A1 WO 2014032393 A1 WO2014032393 A1 WO 2014032393A1 CN 2013000972 W CN2013000972 W CN 2013000972W WO 2014032393 A1 WO2014032393 A1 WO 2014032393A1
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WO
WIPO (PCT)
Prior art keywords
starch
oil
fully biodegradable
biodegradable material
weight
Prior art date
Application number
PCT/CN2013/000972
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English (en)
Chinese (zh)
Inventor
王惠群
Original Assignee
广东益德环保科技有限公司
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Publication date
Application filed by 广东益德环保科技有限公司 filed Critical 广东益德环保科技有限公司
Publication of WO2014032393A1 publication Critical patent/WO2014032393A1/fr

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Classifications

    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • the present invention relates to a composition of a polymer compound, and in particular to a whole biodegradable material and a process for the preparation thereof. Background technique
  • the technical problem to be solved by the present invention is to provide a fully biodegradable material and a preparation method thereof, which are excellent in mechanical properties, biodegradable, and low in price.
  • the technical solutions adopted are as follows:
  • a fully biodegradable material characterized by being made from the following raw materials by weight ratio: starch 30 ⁇ 65%; Vegetable oil polylactic acid 15 ⁇ 50%; copolymer of butylene adipate and butylene terephthalate 10 ⁇ 20% ; compatibilizer 5 ⁇ 30%.
  • the above compatibilizer accounts for 5 to 20% of the total weight of the raw materials.
  • the above starch is one or a combination of both natural starch and modified starch.
  • the natural starch is one or a combination of a plurality of corn starch, tapioca starch, sweet potato starch, sweet potato starch and potato starch.
  • the modified starch is one or more of maleic anhydride grafted starch, phosphated double starch, acetylated distarch phosphate, acetylated double starch adipate and hydroxypropyl distarch phosphate. combination.
  • Starch can be biodegraded, and natural starch is a natural polymer compound that can be completely biodegraded.
  • the natural starch is not only low in cost but also good in degradability.
  • the modified starch can ensure the certain degradation performance of the composite. At the same time, it is more conducive to the improvement of the mechanical properties of the whole biodegradable material.
  • the vegetable oil is used as a plasticizer to plasticize the starch.
  • the plasticized starch has stable performance, and the vegetable oil is not easily precipitated, which is beneficial to the improvement of the mechanical properties of the biodegradable material, especially the toughness, and the starch plasticized by the vegetable oil is resistant to high temperature. Not easy to turn yellow.
  • the above vegetable oil is one or a combination of soybean oil, peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, corn oil, sunflower oil, pine nut oil, tung oil and castor oil.
  • the vegetable oil is soybean oil, and the soybean oil accounts for 10% of the total weight of the raw material, so that not only the fully biodegradable material having excellent properties can be prepared, but also the production cost of the whole biodegradable material can be greatly reduced.
  • PLA polylactic acid
  • the above copolymer of butylene adipate and butylene terephthalate (PBAT for short) has both good ductility and elongation at break, and also has good heat resistance and Impact properties, also have excellent biodegradability.
  • the above polylactic acid, butylene adipate and butylene terephthalate may be commercially available products, and a commercially available general grade may be used.
  • the compatibilizing agent is one of ethylene-vinyl acetate copolymer (abbreviated as EVA), ethylene-acrylic acid copolymer, or a combination of both.
  • the compatibilizing agent is an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer can very well improve the compatibility of starch with PLA and PBAT.
  • the invention also provides a preparation method of the above biodegradable material, the preparation method of the whole biodegradable material comprises the following steps: starch, vegetable oil, polylactic acid, butylene adipate and terephthalate
  • the copolymer of the glycol ester and the compatibilizer are uniformly mixed to obtain a mixture; then the mixture is added to a twin-screw extruder for melt blending to form a material melt; the material melt is from the die of the twin-screw extruder After extrusion, the strips are granulated and granulated to obtain material granules; after the material granules are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder has a screw length to diameter ratio of 35 to 45:1; and the melt blending temperature is 130 to 180 °C.
  • the above-mentioned brace and dicing are the conventional granulation techniques.
  • the present invention has the following advantages:
  • the whole biodegradable material of the invention improves the compatibility of starch with PLA and PBAT through the compatibilizer, plasticizes the starch by vegetable oil, the plasticized starch has stable performance, the vegetable oil is not easily precipitated, and the vegetable oil is plasticized.
  • the starch is resistant to high temperature, so that the raw material can be melt-extruded at a relatively high temperature of 160 to 180 ° C, and the product is not easily yellowed, so that the toughness and impact resistance of the whole biodegradable material of the invention are greatly enhanced, and the performance is stable.
  • the various raw materials of the present invention can interact, so that the whole biodegradable material of the present invention exhibits excellent mechanical properties under the premise of high starch content;
  • the main components of starch, vegetable oil, PLA and PBAT can be biodegraded, so that the whole biodegradable material of the present invention has good degradation performance, and the waste can be finally contaminated by microorganisms in the soil. Decomposition and absorption, low environmental pollution, good environmental and social value;
  • the starch content is relatively high, and since the price is relatively low, especially the natural starch is cheaper and more easily available, which is advantageous for reducing the cost of the whole biodegradable material;
  • the whole biodegradable material of the invention is simple to prepare, easy to implement, easy to operate and control, easy to industrialize, and is advantageous for reducing the cost of the whole biodegradable material.
  • the whole biodegradable material of the invention has excellent and stable performance, is biodegradable, and has low cost, and has good economic and environmental benefits, and has broad application prospects.
  • the whole biodegradable material of the invention is suitable for the fields of plastic packaging materials, agricultural mulch films and disposable tableware, and the whole biodegradable material is used as a raw material, and the existing processing technology can be used to produce plastic packaging materials, agricultural mulch films and disposable tableware. Wait.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to a temperature of 130 ° C, 140, respectively). Each melt blending zone of °C, 150°C, 160°C, 170°C, 180°C, 170°C, 160°C) forms the material melt; the material melt is molded from the twin-screw extruder After the head is extruded, the strips are granulated and granulated to obtain the material granules; after the material granules are dried, the whole biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 40:1.
  • the above maleic anhydride grafted starch can be prepared by the following method: 60 g of corn starch, 2.6 g of maleic anhydride, 100 mL of N,N-dimethylacetamide and 20 mL of toluene were added to a three-necked flask of 250 mL volume, and stirred until homogeneously mixed (mechanically stirred at 130 ° C for 1 hour), allowed to stand.
  • EVA ethylene-vinyl acetate copolymer
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to a temperature of 130 ° C, 140 °). C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 170 ° C, 160 ° C melt blending intervals), forming a material melt; material melt from the twin-screw extruder die After extrusion, the strips are granulated and granulated to obtain material granules; after the material granules are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 40:1.
  • the preparation method of maleic anhydride grafted starch is referred to in Example 1.
  • the copolymer was 12 parts by weight, and the ethylene-vinyl acetate copolymer was 8 parts by weight.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to a temperature of 130 ° (:, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 170 ° C, 160 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder After the die is extruded, the bar is drawn and pelletized to obtain material particles; after the material particles are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder has a screw length to diameter ratio of 35:1.
  • the following parts by weight of raw materials are weighed: 20 parts by weight of tapioca starch, 10 parts by weight of sweet potato starch, 5 parts by weight of pine nut oil, 50 parts by weight of polylactic acid, butylene glycol adipate and butylene terephthalate. 10 parts by weight of the copolymer and 5 parts by weight of the ethylene-vinyl acetate copolymer.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to a temperature of 130° (140, respectively). °C, 150°C, 160°C, 170°C 180°C, 170°C, 160°C, each melt blending zone), forming material melt; The melt is extruded from the die of the twin-screw extruder, and then drawn and pelletized to obtain material particles; after the material particles are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 45:1.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to a temperature of 130 ° C, 140, respectively). °C, 150°C, 160°C, 170°C, 180°C, 170°C, 160°C, each melt blending zone), forming a material melt; material melt from the twin-screw extruder After the head is extruded, the strips are granulated and granulated to obtain the material granules; after the material granules are dried, the whole biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 40:1.
  • the following parts by weight of the raw materials were weighed: 35 parts by weight of phosphate double starch, 15 parts by weight of coconut oil, 20 parts by weight of polylactic acid, and copolymer of butylene adipate and butylene terephthalate 20 Parts by weight, 5 parts by weight of the ethylene-vinyl acetate copolymer, and 5 parts by weight of the ethylene-acrylic acid copolymer.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending. (The mixture is passed through the melt blending zones of 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 170 ° C, 160 ° C, respectively) to form a material melting. The material melt is extruded from the die of the twin-screw extruder, and then drawn and pelletized to obtain material particles; after the material particles are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 40:1.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder and blended (the mixture is sequentially subjected to a temperature of 130 ° C, 140 ° C, 150 ° C 160 ° C, 170 ° C, 180 ° C, 170 ° C, 160 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder mold After the head is extruded, the strips are granulated and granulated to obtain the material granules; after the material granules are dried, the whole biodegradable material is obtained.
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending. (The mixture is passed through the melt blending sections of 130 ° C, 140 ° (:, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 170 ° C, 160 ° C) to form the material. Melt; The material melt is extruded from the die of the twin-screw extruder, and then drawn and pelletized to obtain material particles; after the material particles are dried, a whole biodegradable material is obtained. The screw of the twin-screw extruder used is obtained. The aspect ratio is 40:1.
  • the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to a temperature of 130 ° C, 140, respectively). °C, 150 ° C, 160 ° C 170 ° C, 180 ° C, 170 ° C, 160 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After extrusion, the strips are granulated and granulated to obtain material granules; after the material granules are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 45:1.
  • the following parts by weight of raw materials are weighed: 30 parts by weight of acetylated double starch adipate, 10 parts by weight of tapioca starch, 6 parts by weight of castor oil, 2 parts of corn oil, 30 parts by weight of polylactic acid, and dibutyl adipate. 10 parts by weight of a copolymer of an alcohol ester and a butylene terephthalate, Then, the whole biodegradable material is prepared as follows: All the above raw materials are uniformly mixed to obtain a mixed material; then the mixed material is added to a twin-screw extruder for melt blending.
  • the mixture is passed through the melt blending zones of 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 170 ° C, 160 ° C, respectively) to form a material melting.
  • the material melt is extruded from the die of the twin-screw extruder, and then drawn and pelletized to obtain material particles; after the material particles are dried, a fully biodegradable material is obtained.
  • the twin-screw extruder used had a screw length to diameter ratio of 40:1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un matériau entièrement biodégradable, caractérisé en ce qu'il est fabriqué à partir des matières premières indiquées ci-dessous qui sont présentes selon les rapports pondéraux suivants : 30 à 65 % d'amidon ; 5 à 15 % d'huile végétale ; 15 à 50 % d'acide polylactique ; 10 à 20 % d'un copolymère d'adipate de butylène glycol et de téréphtalate de polybutylène ; et 5 à 30 % d'un agent de compatibilité. L'agent de compatibilité susmentionné représente, de préférence, de 5 à 20 % du poids total des matières premières. Le matériau entièrement biodégradable de la présente invention présente non seulement des performances très intéressantes et stables, mais est également biodégradable et peu coûteux, ce qui signifie qu'il présente un bon équilibre entre avantages économiques et environnementaux, et il peut être utilisé dans un large éventail d'applications. L'invention concerne également un procédé de préparation du matériau entièrement biodégradable susmentionné, qui se révèle facile à mettre en œuvre et à réguler, qui peut facilement être utilisé à l'échelle industrielle et qui conduit à des réductions de coût en matière de fabrication de matériaux entièrement biodégradables.
PCT/CN2013/000972 2012-08-28 2013-08-21 Matériau entièrement biodégradable et son procédé de fabrication WO2014032393A1 (fr)

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CN201210311184.4 2012-08-28
CN2012103111844A CN102796286A (zh) 2012-08-28 2012-08-28 一种全生物降解材料及其制备方法

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CN108586824A (zh) * 2018-05-22 2018-09-28 上海顶贤贸易有限公司 一种可完全降解塑料及其制备方法
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CN108976738A (zh) * 2018-08-07 2018-12-11 吴勇 高性能淀粉／生物降解高分子复合材料和产品的制造方法
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CN112625409A (zh) * 2020-10-23 2021-04-09 威骏(上海)环保包装有限公司 一种生物可降解塑料瓶盖及其制备方法
CN112724472A (zh) * 2020-12-29 2021-04-30 武汉华丽环保科技有限公司 一种高淀粉含量的全生物降解吹膜料及其制备方法
CN113512277A (zh) * 2021-05-10 2021-10-19 上海润文包装材料有限公司 一种新型可降解的超微膜材料配方
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CN113787699A (zh) * 2021-09-14 2021-12-14 保和实业(重庆)有限公司 一种吹膜级全生物降解塑料
CN114957942A (zh) * 2022-05-26 2022-08-30 深圳金藤新材料科技有限公司 一种高效化可降解塑料生产工艺

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