WO2014056293A1 - Biodegradable material, preparation method and use thereof - Google Patents

Biodegradable material, preparation method and use thereof Download PDF

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Publication number
WO2014056293A1
WO2014056293A1 PCT/CN2013/000973 CN2013000973W WO2014056293A1 WO 2014056293 A1 WO2014056293 A1 WO 2014056293A1 CN 2013000973 W CN2013000973 W CN 2013000973W WO 2014056293 A1 WO2014056293 A1 WO 2014056293A1
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Prior art keywords
biodegradable
oil
weight
hydroxybutyric acid
biodegradable material
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PCT/CN2013/000973
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French (fr)
Chinese (zh)
Inventor
王惠群
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广东益德环保科技有限公司
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Publication of WO2014056293A1 publication Critical patent/WO2014056293A1/en

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a composition of a polymer compound, and in particular to a biodegradable material, and a method and application for the preparation of such a biodegradable material.
  • degradable plastics are relatively late materials and are still in a stage of growth and improvement.
  • the existing degradable plastics are biodegradable and environmentally friendly, most of them do not maintain good transparency and/or poor mechanical properties, and the manufactured articles, especially the film products, are easily broken.
  • the technical problem to be solved by the present invention is to provide a biodegradable material, and a preparation method and application of the biodegradable material, which not only have biodegradability, but also have excellent mechanical properties and maintain good performance. Transparency.
  • the technical solutions adopted are as follows:
  • biodegradable material characterized by being made of the following raw materials by weight: 10-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 10 ⁇ 35%; polybutylene succinate 10 ⁇ 35%; Polylactic acid G ⁇ 50% ; vegetable oil 5-25%; plasticizer 1 ⁇ 10%; reaction accelerator 0.02 ⁇ 5%.
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, vegetable oil, plasticizer and reaction accelerator combine to exhibit good elongation at break and good stretching. Strength, overall mechanical properties are better.
  • the above biodegradable material is made of the following raw materials by weight:
  • the above-mentioned weight ratio of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, vegetable oil, plasticizer and reaction accelerator are combined to exhibit good elongation at break. Rate and excellent tensile strength, excellent overall performance.
  • the above-mentioned weight ratio of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutyl succinate The combination of glycol ester, polylactic acid, vegetable oil, plasticizer and reaction accelerator has good elongation at break and very good tensile strength, which is very suitable for making shopping bags in the temple! J mouth.
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate can increase the elongation at break of the biodegradable material of the present invention.
  • the above polylactic acid may be L-type polylactic acid, D-type polylactic acid or LD mixed polylactic acid.
  • Polylactic acid can increase the strength of the biodegradable material of the present invention.
  • the vegetable oil is one or a combination of a plurality of rapeseed oil, castor oil, soybean oil, peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, corn oil, sunflower oil, pine nut oil, and tung oil.
  • rapeseed oil castor oil
  • soybean oil peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, corn oil, sunflower oil, pine nut oil, and tung oil.
  • the above plasticizer is one or a combination of sorbitol, polyethylene glycol, acetylated citric acid and glycerin.
  • the addition of a plasticizer can improve the mobility of the polymer chain, improve the plasticity of the biodegradable material, reduce the brittleness of the biodegradable material, and improve the flexibility of the biodegradable material.
  • the above reaction accelerator is one or a combination of a coupling agent and a catalyst.
  • the coupling agent is a combination of one or both of a silicon germanium compound and an isocyanate compound.
  • the coupling agent is one of ⁇ -aminopropyltriethoxysilane ( ⁇ -550), diphenylcarbamidine diisocyanate (MDI) and polymethyl-p-phenylisocyanate (PMDI for short). Or a combination of many of them.
  • the above catalyst is one or a combination of an organic acid and an inorganic protonic acid.
  • the above catalyst is one of citric acid, adipic acid, succinic acid and hydrochloric acid or a combination of plural kinds thereof.
  • 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer polybutylene succinate, polylactic acid, vegetable oil, plasticizer, reaction accelerator (including coupling agent, catalyst) are commercially available.
  • 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer can be purchased from Tianjin P(3HB-co-4HB) copolyester produced by Yunsheng Biomaterials Co., Ltd.
  • the invention also provides a preparation method of the above biodegradable material, which comprises the steps of: 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, vegetable oil , the plasticizer and the reaction accelerator 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 extruded from the die of the twin-screw extruder After the stripping and pelletizing, the material particles are obtained; after the material particles are dried, a 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 140 to 175 °C.
  • the above-mentioned brace and dicing are the conventional granulation techniques.
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are generally required to be dried before use.
  • the above biodegradable material is used for preparing a biodegradable film, and the biodegradable material is blown by a single screw blown film machine to obtain a biodegradable film.
  • the above-mentioned single screw blown film machine has a screw length to diameter ratio of 25 to 35:1. Since the above biodegradable material has excellent elongation at break and tensile strength and maintains good transparency, it is particularly suitable for producing a biodegradable film. Compared with the prior art, the invention has the following beneficial effects:
  • the main components 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, vegetable oil and polylactic acid can be decomposed by microorganisms under specific conditions, belonging to Completely degradable biomaterials.
  • 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, plasticizer and reaction accelerator are combined to interact and have a certain synergistic effect.
  • the biodegradable material of the present invention exhibits excellent elongation at break and tensile strength, and maintains good transparency and excellent overall performance.
  • the preparation method of the biodegradable material of the invention has the advantages of simple process, easy control, strong operability and low production cost; and after the biodegradable material is simply processed, the biodegradable film can be obtained, which is easy to industrialize and has good performance. Economic benefit, wide Broad application prospects.
  • the biodegradable material of the invention is very suitable for preparing biodegradable film, and the biodegradable film produced has high strength; the shopping bag made of the biodegradable film can be repeatedly used repeatedly, and can be used as a plurality of times after being used for many times. It is used in garbage bags. After being discarded, it is completely absorbed by microorganisms in the soil and absorbed quickly. It has little environmental pollution and has good environmental benefits.
  • the following raw materials by weight are weighed: 18 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 17 parts by weight of polybutylene succinate, 42 parts by weight of polylactic acid, and 16 parts by weight of vegetable oil (All are castor oil), 6 parts by weight of plasticizer (both polyethylene glycol), and 1 part by weight of reaction accelerator (both diphenylmethane diisocyanate).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blown film machine has a screw length to diameter ratio of 25:1.
  • Example 2 First, the following raw materials by weight are weighed: 15 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 15 parts by weight of polybutylene succinate, 50 parts by weight of polylactic acid, and 14 parts by weight of vegetable oil ( All are castor oil), 5 parts by weight of plasticizer (all polyethylene glycol), and 1 part by weight of reaction accelerator (all ⁇ -aminopropyltriethoxysilane).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively).
  • the screw length to diameter ratio of the twin-screw extruder is 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 25:1.
  • the following raw materials by weight are weighed: 19 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 18 parts by weight of polybutylene succinate, 37 parts by weight of polylactic acid, and 17 parts by weight of vegetable oil (All were rapeseed oil), 7 parts by weight of plasticizer (all glycerin), and 2 parts by weight of reaction accelerator (all diphenylformamidine diisocyanate).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, speed during mixing It can be gradually increased) to obtain a mixture; then the mixture is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 ° C, 155 ° C, 160 ° C, 175 °, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 45:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 35:1.
  • the following raw materials by weight are weighed: 10 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 35 parts by weight of polybutylene succinate, 35 parts by weight of polylactic acid, and 10 parts by weight of vegetable oil ( Wherein 5 parts by weight of coconut oil, 5 parts by weight of palm oil), 7 parts by weight of a plasticizer (4 parts by weight of acetylated citric acid, 3 parts by weight of glycerin), and 3 parts by weight of a reaction accelerator (wherein ⁇ -aminopropyl three) 1 part by weight of ethoxysilane and 2 parts by weight of adipic acid).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
  • the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially passed through a temperature of 145 ° (:, 150 °) C, 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After extrusion, the strips are drawn and granulated to obtain material granules; after the material granules are dried, a biodegradable material is obtained.
  • the screw length to diameter ratio of the twin-screw extruder is 35:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 30:1.
  • the following raw materials by weight are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 10 parts by weight of polybutylene succinate, 30 parts by weight of polylactic acid, and 15 parts by weight of vegetable oil (All were pine nut oil), 10 parts by weight of a plasticizer (6 parts by weight of sorbitol, 4 parts by weight of polyethylene glycol), and 5 parts by weight of a reaction accelerator (all citric acid).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 30:1.
  • 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 20 parts by weight, 20 parts by weight of polybutylene succinate, 45 parts by weight of polylactic acid, 5 parts by weight of vegetable oil (all sunflower oil), 5 parts by weight of plasticizer (all acetylated citric acid), reaction 5 parts by weight of accelerator (all polymethyl-p-phenyl isocyanate).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 V, 155, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 25:1.
  • the following raw materials by weight are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 25 parts by weight of polybutylene succinate, 20 parts by weight of polylactic acid, and 15 parts by weight of vegetable oil (All are castor oil), 8 parts by weight of plasticizer (all glycerin), and 2 parts by weight of reaction accelerator (all diphenylformamidine diisocyanate).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • twin-screw extruder Medium melt blending (mixtures are sequentially subjected to melt blending intervals of 145 ° C, 150 ° C, 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C) Forming a material melt; the material melt is extruded from a die of a twin-screw extruder, and then drawn and pelletized to obtain material particles; after the material particles are dried, a biodegradable material is obtained.
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 25:1.
  • the following raw materials by weight are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 20 parts by weight of polybutylene succinate, 25 parts by weight of polylactic acid, and 18 parts by weight of vegetable oil ( There are 10 parts by weight of linseed oil, 8 parts by weight of cottonseed oil, 5 parts by weight of plasticizer (both polyethylene glycol), and 2 parts by weight of reaction accelerator (both diphenylmethane diisocyanate).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 25:1.
  • the following raw materials by weight are weighed: 27 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 30 parts by weight of polybutylene succinate, 15 parts by weight of polylactic acid, and 15 parts by weight of vegetable oil (All are tung oil), 10 parts by weight of plasticizer (all acetylated citric acid), 3 parts by weight of reaction accelerator (including 2 parts by weight of ⁇ -aminopropyltriethoxysilane and 1 part by weight of succinic acid) .
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 45:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 35:1.
  • the following raw materials by weight are weighed: 35 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 35 parts by weight of polybutylene succinate, 10 parts by weight of polylactic acid, and 11 parts by weight of vegetable oil (All are corn oil), 8 parts by weight of plasticizer (all glycerin), reaction 1 part by weight of the vehicle (all adipic acid).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • the twin-screw extruder has a screw length to diameter ratio of 35:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 30:1.
  • the whole biodegradable material as follows: Mix all the above raw materials uniformly to obtain a mixed material (all raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 ° C, and the speed of the premixer is 800 ⁇ 1200 rpm, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process); then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 T: 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), the formation of materials 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 biodegradable material is obtained.
  • the twin-screw extruder has a screw length to diameter ratio of 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN 13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 25:1.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively).
  • the twin-screw extruder has a screw length to diameter ratio of 45:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN 13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 30:1.
  • the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° (:, 175 ° C, 165 ° C, 160 ° C.
  • the screw length to diameter ratio of the twin-screw extruder is 40:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 35:1.
  • the following parts by weight of raw materials are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 30 parts by weight of polybutylene succinate, and 25 parts by weight of vegetable oil (both peanut oil), 10 parts by weight of plasticizer (both polyethylene glycol) and 5 parts by weight of reaction accelerator (both hydrochloric acid).
  • the above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
  • prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800 ⁇ 1200 rpm.
  • the twin-screw extruder has a screw length to diameter ratio of 35:1.
  • the above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
  • the biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film.
  • the single screw blower has a screw length to diameter ratio of 30:1.

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided in the present invention is a biodegradable material prepared from raw materials at the following weight percentages: 10-35% of a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, 10-35% of polybutylene succinate, 0-50% of polylactic acid, 5-25% of a vegetable oil, 1-10% of a plasticizer, and 0.02-5% of a reaction promoter. Also provided in the present invention are a method for preparing the biodegradable material, and the use of the biodegradable material in the preparation of biodegradable films. The biodegradable material of the present invention is a degradable biological material, has an excellent elongation at break and tensile strength, and keeps a relatively good transparency and possesses outstanding comprehensive performances. The preparation method for a biodegradable material of the present invention has a simple technical process, easy control, high operability, and low production costs; in addition, after a simple processing of the biodegradable material, a biodegradable film can be obtained, and thus the industrial production is facilitated, having good economic benefits and a wide prospect of application.

Description

一种生物降解材料及其制备方法和应用 技术领域  Biodegradable material, preparation method and application thereof
本发明涉及高分子化合物的组合物， 具体涉及一种生物降解材 料， 以及这种生物降解材料的制备方法和应用。  The present invention relates to a composition of a polymer compound, and in particular to a biodegradable material, and a method and application for the preparation of such a biodegradable material.
背景技术 Background technique
自 20世纪 30年代塑料材料投入使用以来， 以其质轻、 价廉、 外 表光洁美观、 耐腐蚀、 生产工艺简单等卓越特性， 广泛应用于国民经 济各部门和人民生活各领域。 由于塑料的大量应用， 废弃塑料制品与 日俱增， 而塑料大多性能稳定， 因此出现了所谓的白色污染， 给环境 带来了很大的危害。近年来， 人们对废弃塑料的治理采取了积极的措 施， 例如， 塑料包装材料的减量化， 多次重复使用， 以及回收再利用 等等。 然而， 对于那些不易回收、 回收价值不大或者回收利用在经济 上难以运行的制品， 如购物袋、 一次性餐具、 农用地膜、 医用塑料制 品等， 采用降解塑料制作则更为有利。  Since the introduction of plastic materials in the 1930s, it has been widely used in various sectors of the national economy and people's lives due to its excellent features such as light weight, low price, clean appearance, corrosion resistance and simple production process. Due to the large number of applications of plastics, waste plastic products are increasing day by day, and most of the plastics are stable in performance, so so-called white pollution has occurred, which has brought great harm to the environment. In recent years, positive measures have been taken in the management of waste plastics, such as the reduction of plastic packaging materials, repeated use, and recycling. However, it is more advantageous to use degradable plastics for products that are not easily recycled, have little recycling value, or are economically difficult to operate, such as shopping bags, disposable tableware, agricultural mulch films, medical plastic products, and the like.
但是降解塑料是较晚发展起来的材料， 目前还处于一个成长、完 善的阶段。现有的降解塑料虽然具有生物可降解性，有利于环境保护， 但大多不能保持良好的透明性， 且 /或力学性能不佳， 所制作的制品 特别是薄膜类制品容易破损。  However, degradable plastics are relatively late materials and are still in a stage of growth and improvement. Although the existing degradable plastics are biodegradable and environmentally friendly, most of them do not maintain good transparency and/or poor mechanical properties, and the manufactured articles, especially the film products, are easily broken.
发明内容 Summary of the invention
本发明所要解决的技术问题是提供一种生物降解材料，以及这种 生物降解材料的制备方法和应用，这种生物降解材料不但具有生物降 解性， 而且具有优异的力学性能， 并保持较好的透明性。采用的技术 方案如下：  The technical problem to be solved by the present invention is to provide a biodegradable material, and a preparation method and application of the biodegradable material, which not only have biodegradability, but also have excellent mechanical properties and maintain good performance. Transparency. The technical solutions adopted are as follows:
一种生物降解材料， 其特征在于由下述重量百分比的原料制成： 3-羟基丁酸和 4-羟基丁酸共聚物 10~35%； 聚丁二酸丁二醇酯 10〜35%； 聚乳酸 G〜50%; 植物油 5-25%； 增塑剂 1〜10%； 反应促进剂 0.02〜5%。 上述 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁二醇酯、 植 物油、增塑剂和反应促进剂组合在一起， 体现出良好的断裂伸长率和 良好的拉伸强度， 整体力学性能较好。 优选上述生物降解材料由下述重量百分比的原料制成: a biodegradable material characterized by being made of the following raw materials by weight: 10-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 10~35%; polybutylene succinate 10~35%; Polylactic acid G~50% ; vegetable oil 5-25%; plasticizer 1~10%; reaction accelerator 0.02~5%. The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, vegetable oil, plasticizer and reaction accelerator combine to exhibit good elongation at break and good stretching. Strength, overall mechanical properties are better. Preferably, the above biodegradable material is made of the following raw materials by weight:
3-羟基丁酸和 4-羟基丁酸共聚物 15〜22%； 聚丁二酸丁二醇酯 15~22%； 聚乳酸 25〜50%； 植物油 14~25%； 增塑剂 5~10%； 反应促进剂 1〜5%。 上述重量配比的 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁 二醇酯、 聚乳酸、 植物油、 增塑剂和反应促进剂组合在一起， 体现良 好的断裂伸长率和优异的拉伸强度， 综合性能优异。  3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 15~22%; polybutylene succinate 15~22%; polylactic acid 25~50%; vegetable oil 14~25%; plasticizer 5~10 %; reaction accelerator 1 to 5%. The above-mentioned weight ratio of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, vegetable oil, plasticizer and reaction accelerator are combined to exhibit good elongation at break. Rate and excellent tensile strength, excellent overall performance.
3-羟基丁酸和 4-羟基丁酸共聚物 15〜19%； 聚丁二酸丁二醇酯 15~19%； 聚乳酸 37-50%； 植物油 14~18%； 增塑剂 5~7%； 反应促进剂 1~2%。 上述重量配比的 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁 二醇酯、 聚乳酸、 植物油、 增塑剂和反应促进剂组合在一起， 具有良 好的断裂伸长率和非常优异的拉伸强度，非常适合于制作购物塑料袋 寺市 !J口口。 上述 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁二醇酯能够 提高本发明生物降解材料的断裂伸长率。 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 15~19%; polybutylene succinate 15~19%; polylactic acid 37-50%; vegetable oil 14~18%; plasticizer 5~7 %; reaction accelerator 1~2%. The above-mentioned weight ratio of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutyl succinate The combination of glycol ester, polylactic acid, vegetable oil, plasticizer and reaction accelerator has good elongation at break and very good tensile strength, which is very suitable for making shopping bags in the temple! J mouth. The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate can increase the elongation at break of the biodegradable material of the present invention.
上述聚乳酸可采用 L型聚乳酸、 D型聚乳酸或者 LD混合型聚乳 酸。 聚乳酸能够提高本发明生物降解材料的强度。  The above polylactic acid may be L-type polylactic acid, D-type polylactic acid or LD mixed polylactic acid. Polylactic acid can increase the strength of the biodegradable material of the present invention.
优选上述植物油为菜籽油、 蓖麻油、 大豆油、 花生油、 椰子油、 棕榈油、 亚麻油、 棉籽油、 玉米油、 葵花籽油、 松子油和桐油中的一 种或其中多种的组合。加入植物油， 通过植物油中的反应活性基团与 基体树脂 （即 3-羟基丁酸和 4-羟基丁酸共聚物以及聚丁二酸丁二醇 酯） 中的活性官能团的相互作用， 以达到增容目的。  Preferably, the vegetable oil is one or a combination of a plurality of rapeseed oil, castor oil, soybean oil, peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, corn oil, sunflower oil, pine nut oil, and tung oil. Adding vegetable oil, through the interaction of the reactive groups in the vegetable oil with the reactive functional groups in the matrix resin (ie 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate) The purpose.
上述增塑剂为山梨醇、聚乙二醇、 乙酰化柠檬酸和甘油中的一种 或其中多种的组合。 加入增塑剂， 能够提高聚合物链的移动性能， 使 生物降解材料的可塑效果得到提高， 降低生物降解材料的脆性， 提高 生物降解材料的柔性。  The above plasticizer is one or a combination of sorbitol, polyethylene glycol, acetylated citric acid and glycerin. The addition of a plasticizer can improve the mobility of the polymer chain, improve the plasticity of the biodegradable material, reduce the brittleness of the biodegradable material, and improve the flexibility of the biodegradable material.
优选上述反应促进剂为偶联剂和催化剂中的一种或两者的组合。 优选上述偶联剂为硅垸化合物和异氰酸酯化合物中的一种或两 者的组合。 作为优选， 上述偶联剂为 γ-氨丙基三乙氧基硅垸 (ΚΗ-550), 二苯基甲垸二异氰酸酯 （MDI) 和聚甲基对苯异氰酸酯 (简称 PMDI) 中的一种或者其中多种的组合。  Preferably, the above reaction accelerator is one or a combination of a coupling agent and a catalyst. Preferably, the coupling agent is a combination of one or both of a silicon germanium compound and an isocyanate compound. Preferably, the coupling agent is one of γ-aminopropyltriethoxysilane (ΚΗ-550), diphenylcarbamidine diisocyanate (MDI) and polymethyl-p-phenylisocyanate (PMDI for short). Or a combination of many of them.
优选上述催化剂为有机酸和无机质子酸中的一种或两者的组合。 作为优选， 上述催化剂为柠檬酸、 己二酸、 丁二酸和盐酸中的一种或 者其中多种的组合。  Preferably, the above catalyst is one or a combination of an organic acid and an inorganic protonic acid. Preferably, the above catalyst is one of citric acid, adipic acid, succinic acid and hydrochloric acid or a combination of plural kinds thereof.
上述 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁二醇酯、 聚 乳酸、 植物油、 增塑剂、 反应促进剂（包括偶联剂、 催化剂）均可在 市场上购买到， 其中 3-羟基丁酸和 4-羟基丁酸共聚物可选购天津国 韵生物材料有限公司生产的 P(3HB-co-4HB)共聚酯。 The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, vegetable oil, plasticizer, reaction accelerator (including coupling agent, catalyst) are commercially available. To, among them, 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer can be purchased from Tianjin P(3HB-co-4HB) copolyester produced by Yunsheng Biomaterials Co., Ltd.
本发明还提供上述生物降解材料的一种制备方法，其特征在于包 括下述步骤： 将 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁二醇 酯、聚乳酸、植物油、增塑剂和反应促进剂混合均匀，得到混合物料; 然后将混合物料加入到双螺杆挤出机中熔融共混， 形成物料熔体； 物 料熔体从双螺杆挤出机的模头挤出后进行拉条、切粒，得到物料颗粒; 物料颗粒经干燥处理后， 得到生物降解材料。优选双螺杆挤出机的螺 杆长径比为 35〜45: 1， 熔融共混的温度为 140〜175°C。 上述拉条、 切 粒属现有常规的造粒技术手段。 上述 3-羟基丁酸和 4-羟基丁酸共聚 物和聚丁二酸丁二醇酯使用前一般需要先进行干燥处理。 上述生物降解材料在制备生物降解薄膜中的应用，将所述生物降 解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。上述单螺杆吹膜机 的螺杆长径比为 25〜35: 1。 由于上述生物降解材料具有优异的断裂伸 长率和拉伸强度， 并且保持了较好的透明性， 因而特别适合制造生物 降解薄膜。 本发明与现有技术相比， 具有如下有益效果： The invention also provides a preparation method of the above biodegradable material, which comprises the steps of: 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, vegetable oil , the plasticizer and the reaction accelerator 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 extruded from the die of the twin-screw extruder After the stripping and pelletizing, the material particles are obtained; after the material particles are dried, a biodegradable material is obtained. Preferably, the twin-screw extruder has a screw length to diameter ratio of 35 to 45: 1, and the melt blending temperature is 140 to 175 °C. The above-mentioned brace and dicing are the conventional granulation techniques. The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are generally required to be dried before use. The above biodegradable material is used for preparing a biodegradable film, and the biodegradable material is blown by a single screw blown film machine to obtain a biodegradable film. The above-mentioned single screw blown film machine has a screw length to diameter ratio of 25 to 35:1. Since the above biodegradable material has excellent elongation at break and tensile strength and maintains good transparency, it is particularly suitable for producing a biodegradable film. Compared with the prior art, the invention has the following beneficial effects:
本发明生物降解材料中， 主要组分 3-羟基丁酸和 4-羟基丁酸共 聚物、 聚丁二酸丁二醇酯、 植物油以及聚乳酸， 在特定的条件下都可 被微生物分解， 属于完全可降解生物材料。 此外， 3-羟基丁酸和 4- 羟基丁酸共聚物、 聚丁二酸丁二醇酯、 聚乳酸、 增塑剂以及反应促进 剂组合在一起， 能够相互作用， 具有一定的协同作用， 使得本发明的 生物降解材料体现出优异的断裂伸长率和拉伸强度，并且保持了较好 的透明性， 综合性能优异。  In the biodegradable material of the present invention, the main components 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, vegetable oil and polylactic acid can be decomposed by microorganisms under specific conditions, belonging to Completely degradable biomaterials. In addition, 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, plasticizer and reaction accelerator are combined to interact and have a certain synergistic effect. The biodegradable material of the present invention exhibits excellent elongation at break and tensile strength, and maintains good transparency and excellent overall performance.
本发明生物降解材料的制备方法工艺简单， 易于控制， 可操作性 强， 生产成本低廉； 并且将生物降解材料再经简单的加工后， 就可以 得到生物降解薄膜， 易于工业化生产并具有很好的经济效益， 具有广 阔的应用前景。 The preparation method of the biodegradable material of the invention has the advantages of simple process, easy control, strong operability and low production cost; and after the biodegradable material is simply processed, the biodegradable film can be obtained, which is easy to industrialize and has good performance. Economic benefit, wide Broad application prospects.
本发明生物降解材料非常适用于制备生物降解薄膜，制成的生物 降解薄膜具有很高的强度；这种生物降解薄膜制成的购物袋可多次反 复使用， 而且在多次使用后仍可以作为垃圾袋使用， 废弃后被土壤中 的微生物完全分解快速吸收， 对环境污染小， 具有很好的环境效益。 具体实施方式 实施例 1  The biodegradable material of the invention is very suitable for preparing biodegradable film, and the biodegradable film produced has high strength; the shopping bag made of the biodegradable film can be repeatedly used repeatedly, and can be used as a plurality of times after being used for many times. It is used in garbage bags. After being discarded, it is completely absorbed by microorganisms in the soil and absorbed quickly. It has little environmental pollution and has good environmental benefits. DETAILED DESCRIPTION OF THE INVENTION Example 1
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 18重量份， 聚丁二酸丁二醇酯 17重量份， 聚乳酸 42重量份， 植物 油 16重量份 （均为蓖麻油）， 增塑剂 6重量份 （均为聚乙二醇）， 反 应促进剂 1重量份 （均为二苯基甲烷二异氰酸酯）。 上述 3-羟基丁酸 和 4-羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行干燥处理。  First, the following raw materials by weight are weighed: 18 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 17 parts by weight of polybutylene succinate, 42 parts by weight of polylactic acid, and 16 parts by weight of vegetable oil ( All are castor oil), 6 parts by weight of plasticizer (both polyethylene glycol), and 1 part by weight of reaction accelerator (both diphenylmethane diisocyanate). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155 °C、 160°C、 175°C、 165°C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40: 1。上述拉条、切粒属现有常规的造粒技术手段， 在此不作更详细说明。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After the stripping, the pelletizing is performed to obtain the material particles; after the material particles are dried, the biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 40:1. The above-mentioned brace and pelletizing are conventional conventional granulation techniques and will not be described in further detail herein.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 25:1。 实施例 2 首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 15重量份， 聚丁二酸丁二醇酯 15重量份， 聚乳酸 50重量份， 植物 油 14重量份 （均为蓖麻油）， 增塑剂 5重量份 （均为聚乙二醇）， 反 应促进剂 1重量份（均为 γ-氨丙基三乙氧基硅垸）。上述 3-羟基丁酸 和 4-羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行干燥处理。 The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blown film machine has a screw length to diameter ratio of 25:1. Example 2 First, the following raw materials by weight are weighed: 15 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 15 parts by weight of polybutylene succinate, 50 parts by weight of polylactic acid, and 14 parts by weight of vegetable oil ( All are castor oil), 5 parts by weight of plasticizer (all polyethylene glycol), and 1 part by weight of reaction accelerator (all γ-aminopropyltriethoxysilane). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155°C、 160°C、 175°C、 165° (、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40: 1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° C, 175 ° C, 165 ° (, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After the stripping, pelletizing, the material particles are obtained; after the material particles are dried, a biodegradable material is obtained. The screw length to diameter ratio of the twin-screw extruder is 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 25: 1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 25:1.
实施例 3 Example 3
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 19重量份， 聚丁二酸丁二醇酯 18重量份， 聚乳酸 37重量份， 植物 油 17重量份 （均为菜籽油）， 增塑剂 7重量份 （均为甘油）， 反应促 进剂 2重量份 （均为二苯基甲垸二异氰酸酯）。 上述 3-羟基丁酸和 4- 羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行干燥处理。  First, the following raw materials by weight are weighed: 19 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 18 parts by weight of polybutylene succinate, 37 parts by weight of polylactic acid, and 17 parts by weight of vegetable oil ( All were rapeseed oil), 7 parts by weight of plasticizer (all glycerin), and 2 parts by weight of reaction accelerator (all diphenylformamidine diisocyanate). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145 °C、 150°C、 155 °C、 160°C、 175°C , 165°C 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。双螺杆挤出 机的螺杆长径比为 45:1。 Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, speed during mixing It can be gradually increased) to obtain a mixture; then the mixture is added to a twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 ° C, 155 ° C, 160 ° C, 175 °, respectively). C, 165 ° C 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die extrusion, granulation, to obtain material particles After the material particles are dried, a biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 45:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 35: 1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 35:1.
实施例 4 Example 4
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 10重量份， 聚丁二酸丁二醇酯 35重量份， 聚乳酸 35重量份， 植物 油 10重量份（其中椰子油 5重量份、棕榈油 5重量份）， 增塑剂 7重 量份 （其中乙酰化柠檬酸 4重量份、 甘油 3重量份）， 反应促进剂 3 重量份 （其中 γ-氨丙基三乙氧基硅烷 1重量份、 己二酸 2重量份）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先 进行干燥处理。  First, the following raw materials by weight are weighed: 10 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 35 parts by weight of polybutylene succinate, 35 parts by weight of polylactic acid, and 10 parts by weight of vegetable oil ( Wherein 5 parts by weight of coconut oil, 5 parts by weight of palm oil), 7 parts by weight of a plasticizer (4 parts by weight of acetylated citric acid, 3 parts by weight of glycerin), and 3 parts by weight of a reaction accelerator (wherein γ-aminopropyl three) 1 part by weight of ethoxysilane and 2 parts by weight of adipic acid). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145 ° (：、 150°C、 155 °C、 160°C、 175°C、 165°C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。双螺杆挤出 机的螺杆长径比为 35:1。 上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。 Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially passed through a temperature of 145 ° (:, 150 °) C, 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After extrusion, the strips are drawn and granulated to obtain material granules; after the material granules are dried, a biodegradable material is obtained. The screw length to diameter ratio of the twin-screw extruder is 35:1. The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 30:1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 30:1.
实施例 5 Example 5
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 30重量份， 聚丁二酸丁二醇酯 10重量份， 聚乳酸 30重量份， 植物 油 15重量份 （均为松子油）， 增塑剂 10重量份 （其中山梨醇 6重量 份、 聚乙二醇 4重量份）， 反应促进剂 5重量份（均为柠檬酸）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行 干燥处理。  First, the following raw materials by weight are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 10 parts by weight of polybutylene succinate, 30 parts by weight of polylactic acid, and 15 parts by weight of vegetable oil ( All were pine nut oil), 10 parts by weight of a plasticizer (6 parts by weight of sorbitol, 4 parts by weight of polyethylene glycol), and 5 parts by weight of a reaction accelerator (all citric acid). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混^^， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155°C、 160°C、 175°C、 165°C , 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40: 1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~ 1200 rpm, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150, respectively). °C, 155°C, 160°C, 175°C, 165°C, 160°C, 150°C, each melt blending zone), forming a material melt; material melt from the twin-screw extruder After the head is extruded, the strip is drawn and pelletized to obtain material particles; after the material particles are dried, a biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 30:1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 30:1.
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 20重量份， 聚丁二酸丁二醇酯 20重量份， 聚乳酸 45重量份， 植物 油 5重量份（均为葵花籽油），增塑剂 5重量份（均为乙酰化柠檬酸）， 反应促进剂 5重量份 （均为聚甲基对苯异氰酸酯）。 上述 3-羟基丁酸 和 4-羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行干燥处理。 First, weigh the following parts by weight: 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 20 parts by weight, 20 parts by weight of polybutylene succinate, 45 parts by weight of polylactic acid, 5 parts by weight of vegetable oil (all sunflower oil), 5 parts by weight of plasticizer (all acetylated citric acid), reaction 5 parts by weight of accelerator (all polymethyl-p-phenyl isocyanate). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800〜1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145 °C、 150V , 155 °C、 160°C、 175 °C、 165 °C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。双螺杆挤出 机的螺杆长径比为 40: 1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 V, 155, respectively). °C, 160 °C, 175 °C, 165 °C, 160 °C, 150 °C for each melt blending zone), forming a material melt; after the material melt is extruded from the die of the twin-screw extruder The strips are granulated and granulated to obtain material granules; after the material granules are dried, a biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 25: 1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 25:1.
实施例 7 Example 7
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 30重量份， 聚丁二酸丁二醇酯 25重量份， 聚乳酸 20重量份， 植物 油 15重量份 （均为蓖麻油）， 增塑剂 8重量份 （均为甘油）， 反应促 进剂 2重量份 （均为二苯基甲垸二异氰酸酯）。 上述 3-羟基丁酸和 4- 羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行干燥处理。  First, the following raw materials by weight are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 25 parts by weight of polybutylene succinate, 20 parts by weight of polylactic acid, and 15 parts by weight of vegetable oil ( All are castor oil), 8 parts by weight of plasticizer (all glycerin), and 2 parts by weight of reaction accelerator (all diphenylformamidine diisocyanate). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145 °C、 150°C、 155 °C、 160°C、 175°C、 165°C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40: 1。 Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the speed can be gradually increased during the mixing process), the mixture is obtained; then the mixture is added to the twin-screw extruder Medium melt blending (mixtures are sequentially subjected to melt blending intervals of 145 ° C, 150 ° C, 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C) Forming a material melt; the material melt is extruded from a die of a twin-screw extruder, and then drawn and pelletized to obtain material particles; after the material particles are dried, a biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 25:1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 25:1.
实施例 8 Example 8
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 30重量份， 聚丁二酸丁二醇酯 20重量份， 聚乳酸 25重量份， 植物 油 18重量份 （其中亚麻油 10重量份、 棉籽油 8重量份）， 增塑剂 5 重量份 （均为聚乙二醇）， 反应促进剂 2重量份 （均为二苯基甲烷二 异氰酸酯）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚丁二酸丁二醇 酯使用前先进行干燥处理。  First, the following raw materials by weight are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 20 parts by weight of polybutylene succinate, 25 parts by weight of polylactic acid, and 18 parts by weight of vegetable oil ( There are 10 parts by weight of linseed oil, 8 parts by weight of cottonseed oil, 5 parts by weight of plasticizer (both polyethylene glycol), and 2 parts by weight of reaction accelerator (both diphenylmethane diisocyanate). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155°C、 160°C、 175°C、 165°C、 160°C , 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40:1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After the stripping, the pelletizing is performed to obtain the material particles; after the material particles are dried, the biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。 将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 25: 1。 The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards. The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 25:1.
实施例 9 Example 9
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 27重量份， 聚丁二酸丁二醇酯 30重量份， 聚乳酸 15重量份， 植物 油 15重量份 （均为桐油）， 增塑剂 10重量份 （均为乙酰化柠檬酸）， 反应促进剂 3重量份（其中 γ-氨丙基三乙氧基硅垸 2重量份、丁二酸 1重量份）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚丁二酸丁二醇 酯使用前先进行干燥处理。  First, the following raw materials by weight are weighed: 27 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 30 parts by weight of polybutylene succinate, 15 parts by weight of polylactic acid, and 15 parts by weight of vegetable oil ( All are tung oil), 10 parts by weight of plasticizer (all acetylated citric acid), 3 parts by weight of reaction accelerator (including 2 parts by weight of γ-aminopropyltriethoxysilane and 1 part by weight of succinic acid) . The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155°C、 160°C、 175 t；、 165 °C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 45:1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° C, 175 t;, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After the stripping, the pelletizing is performed to obtain the material particles; after the material particles are dried, the biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 45:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 35: 1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 35:1.
实施例 10 Example 10
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 35重量份， 聚丁二酸丁二醇酯 35重量份， 聚乳酸 10重量份， 植物 油 11重量份 （均为玉米油）， 增塑剂 8重量份 （均为甘油）， 反应促 进剂 1重量份 （均为己二酸）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物 和聚丁二酸丁二醇酯使用前先进行干燥处理。 First, the following raw materials by weight are weighed: 35 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 35 parts by weight of polybutylene succinate, 10 parts by weight of polylactic acid, and 11 parts by weight of vegetable oil ( All are corn oil), 8 parts by weight of plasticizer (all glycerin), reaction 1 part by weight of the vehicle (all adipic acid). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150T：、 155 °C、 160°C、 175°C、 165 °C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 35: 1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 T: 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die extrusion After the stripping and pelletizing, the material particles are obtained; after the material particles are dried, a biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 35:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 30:1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 30:1.
实施例 11 Example 11
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 35重量份， 聚丁二酸丁二醇酯 35重量份， 植物油 20重量份 （均为 蓖麻油）， 增塑剂 5重量份（均为甘油）， 反应促进剂 5重量份（均为 二苯基甲垸二异氰酸酯）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚 丁二酸丁二醇酯使用前先进行干燥处理。  First, weighed the following raw materials by weight: 35 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 35 parts by weight of polybutylene succinate, 20 parts by weight of vegetable oil (both castor oil), 5 parts by weight of the plasticizer (all glycerin) and 5 parts by weight of the reaction accelerator (both diphenylformamidine diisocyanate). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate were dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀， 得到混合物料（可将所有原料在预混机中进行预混合， 混合的初 始温度为 40°C， 预混机的转速为 800〜1200转 /分钟， 混合 30分钟， 混合过程中转速可逐渐提高）； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145 °C、 150T：、 155°C、 160°C , 175 °C、 165°C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40: 1。 Then, prepare the whole biodegradable material as follows: Mix all the above raw materials uniformly to obtain a mixed material (all raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 ° C, and the speed of the premixer is 800~1200 rpm, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process); then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C, 150 T: 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), the formation of materials 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 biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN 13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN 13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 25: 1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 25:1.
实施例 12 Example 12
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 35重量份， 聚丁二酸丁二醇酯 29.98重量份， 植物油 25重量份 （其 中松子油 15重量份、 桐油 10重量份）， 增塑剂 10重量份（其中山梨 醇 6重量份、 聚乙二醇 4重量份）， 反应促进剂 0.02重量份 （均为 γ- 氨丙基三乙氧基硅垸）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚丁 二酸丁二醇酯使用前先进行干燥处理。  First, weigh the following parts by weight: 35 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 29.98 parts by weight of polybutylene succinate, 25 parts by weight of vegetable oil (15 parts by weight of pine nut oil) 10 parts by weight of tung oil), 10 parts by weight of plasticizer (6 parts by weight of sorbitol, 4 parts by weight of polyethylene glycol), and 0.02 parts by weight of reaction accelerator (both gamma-aminopropyltriethoxysilane) ). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145 °C、 150°C 155 °C、 160°C、 175°C、 165°C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 45:1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die extrusion After the stripping and pelletizing, the material particles are obtained; after the material particles are dried, a biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 45:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN 13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN 13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 30: 1。 实施例 13 The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 30:1. Example 13
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 35重量份， 聚丁二酸丁二醇酯 35重量份， 植物油 25重量份 （均为 大豆油），增塑剂 1重量份（均为聚乙二醇），反应促进剂 4重量份（其 中二苯基甲垸二异氰酸酯 3重量份、 丁二酸 1重量份）。 上述 3-羟基 丁酸和 4-羟基丁酸共聚物和聚丁二酸丁二醇酯使用前先进行干燥处 理。  First, weigh out the following raw materials by weight: 35 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 35 parts by weight of polybutylene succinate, and 25 parts by weight of vegetable oil (both soybean oil), 1 part by weight of plasticizer (all polyethylene glycol), 4 parts by weight of a reaction accelerator (in which 3 parts by weight of diphenylformamidine diisocyanate and 1 part by weight of succinic acid). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are subjected to a drying treatment before use.
然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800〜1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155 °C、 160° (：、 175°C、 165°C、 160°C . 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 40:1。  Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° (:, 175 ° C, 165 ° C, 160 ° C. 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After extrusion, the strips are drawn and granulated to obtain material granules; after the material granules are dried, a biodegradable material is obtained. The screw length to diameter ratio of the twin-screw extruder is 40:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 35: 1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 35:1.
实施例 14 Example 14
首先， 称取以下重量份的原料： 3-羟基丁酸和 4-羟基丁酸共聚物 30重量份， 聚丁二酸丁二醇酯 30重量份， 植物油 25重量份 （均为 花生油）， 增塑剂 10重量份 （均为聚乙二醇）， 反应促进剂 5重量份 (均为盐酸）。 上述 3-羟基丁酸和 4-羟基丁酸共聚物和聚丁二酸丁二 醇酯使用前先进行干燥处理。 然后， 按以下步骤制备全生物降解材料： 将上述所有原料混合均 匀 （可将所有原料在预混机中进行预混合， 混合的初始温度为 40°C， 预混机的转速为 800~1200转 /分钟， 混合 30分钟， 混合过程中转速 可逐渐提高）， 得到混合物料； 然后将混合物料加入到双螺杆挤出机 中熔融共混 （混合物料依次经过温度分别为 145°C、 150°C、 155°C、 160'C、 175°C、 165°C、 160°C、 150°C的各熔融共混区间）， 形成物料 熔体； 物料熔体从双螺杆挤出机的模头挤出后进行拉条、 切粒， 得到 物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 双螺杆挤出 机的螺杆长径比为 35:1。 First, the following parts by weight of raw materials are weighed: 30 parts by weight of 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 30 parts by weight of polybutylene succinate, and 25 parts by weight of vegetable oil (both peanut oil), 10 parts by weight of plasticizer (both polyethylene glycol) and 5 parts by weight of reaction accelerator (both hydrochloric acid). The above 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer and polybutylene succinate are dried before use. Then, prepare the whole biodegradable material as follows: Mix all the above materials evenly (all the raw materials can be pre-mixed in the premixer, the initial temperature of the mixing is 40 °C, and the speed of the premixer is 800~1200 rpm. /min, mixing for 30 minutes, the rotation speed can be gradually increased during the mixing process), and the mixture is obtained; then the mixture is added to the twin-screw extruder for melt blending (the mixture is sequentially subjected to temperatures of 145 ° C and 150 ° C, respectively). , 155 ° C, 160 ° C, 175 ° C, 165 ° C, 160 ° C, 150 ° C each melt blending interval), forming a material melt; material melt from the twin-screw extruder die After the stripping, the pelletizing is performed to obtain the material particles; after the material particles are dried, the biodegradable material is obtained. The twin-screw extruder has a screw length to diameter ratio of 35:1.
上述生物降解材料能够符合美国 ASTMD6400 以及欧盟 EN13432降解标准。  The above biodegradable materials can meet the American ASTM D6400 and EU EN13432 degradation standards.
将上述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 单螺杆吹膜机的螺杆长径比为 30:1。  The biodegradable material is blown through a single screw blown film machine to obtain a biodegradable film. The single screw blower has a screw length to diameter ratio of 30:1.
将实施例 1~14制备的生物降解薄膜按照 GB 1040-79进行断裂伸 长率和拉伸强度的测试， 其测试结果如表 1所示。 表 1 The biodegradable films prepared in Examples 1 to 14 were tested for elongation at break and tensile strength in accordance with GB 1040-79, and the test results are shown in Table 1. Table 1
Figure imgf000016_0001
8 286 24
Figure imgf000016_0001
8 286 24
9 272 25  9 272 25
10 280 22  10 280 22
11 539 20.5  11 539 20.5
12 534 21  12 534 21
13 519 20  13 519 20
14 519 20 从表 1的测试结果可见，实施例 1~6制备的生物降解材料用在生 产生物降解薄膜中，生产的生物降解薄膜体现出优异的拉伸强度和良 好的断裂伸长率， 非常适合于购物塑料袋等领域； 实施例 11~14制备 的生物降解材料用在生产生物降解薄膜中，生产的生物降解薄膜体现 出优异的断裂伸长率和良好的拉伸强度，适合于对断裂伸长率有较高 要求领域， 如保鲜膜； 实施例 7〜10介于上述两者之间， 适合于对断 裂伸长率和拉伸强度有一定要求但要求都不高的领域。  14 519 20 It can be seen from the test results in Table 1 that the biodegradable materials prepared in Examples 1 to 6 are used in the production of biodegradable films, and the biodegradable film produced exhibits excellent tensile strength and good elongation at break, very Suitable for shopping in plastic bags and other fields; the biodegradable materials prepared in Examples 11 to 14 are used in the production of biodegradable films, and the biodegradable film produced exhibits excellent elongation at break and good tensile strength, and is suitable for fracture. Elongation has a higher demand area, such as wrap film; Examples 7 to 10 are between the above two, and are suitable for fields requiring certain elongation at break and tensile strength but not required.

Claims

权利要求述 Claims
1、 一种生物降解材料， 其特征在于由下述重量百分比的原料制 1. A biodegradable material, characterized in that it is made of the following raw materials in weight percentages
3-羟基丁酸和 4-羟基丁酸共聚物 10-35%； 聚丁二酸丁二醇酯 10-35%； 聚乳酸 0- 50%； 植物油 5-25%； 增塑剂 1- 10%； 反应促进剂 0.02~5%。3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 10-35%; polybutylene succinate 10-35%; polylactic acid 0-50%; vegetable oil 5-25%; plasticizer 1-10 %; reaction accelerator 0.02~5%.
2、 根据权利要求 1所述的生物降解材料 其特征在于由下述重 ：百分比的原料制成： 2. The biodegradable material according to claim 1, characterized in that it is made of the following raw materials in weight percentages:
3-羟基丁酸和 4-羟基丁酸共聚物 15-22%； 聚丁二酸丁二醇酯 15-22%； 聚乳酸 25-50%； 植物油 14- 25%； 增塑剂 5-10%； 反应促进剂 1~5%。 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 15-22%; polybutylene succinate 15-22%; polylactic acid 25-50%; vegetable oil 14-25%; plasticizer 5-10 %; reaction accelerator 1~5%.
3、 根据权利要求 2所述的生物降解材料 其特征在于由下述重 ：百分比的原料制成： 3. The biodegradable material according to claim 2, characterized in that it is made of the following weight: percentage of raw materials:
3-羟基丁酸和 4-羟基丁酸共聚物 15- 19%； 聚丁二酸丁二醇酯 15-19%； 聚乳酸 37-50%； 植物油 14-18%； 增塑剂 5-7%； 反应促进剂 卜 2%。 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer 15-19%; polybutylene succinate 15-19%; polylactic acid 37-50%; vegetable oil 14-18%; plasticizer 5-7 %; reaction accelerator bu 2%.
4、根据权利要求 1一 3任一项所述的生物降解材料，其特征在于: 所述植物油为菜籽油、 蓖麻油、 大豆油、 花生油、 椰子油、 棕榈油、 亚麻油、 棉籽油、 玉米油、 葵花籽油、 松子油和桐油中的一种或其中 多种的组合。 4. The biodegradable material according to any one of claims 1 to 3, characterized in that: the vegetable oil is rapeseed oil, castor oil, soybean oil, peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, One or a combination of corn oil, sunflower oil, pine nut oil and tung oil.
5、根据权利要求 1一 3任一项所述的生物降解材料，其特征在于: 所述增塑剂为山梨醇、聚乙二醇、 乙酰化柠檬酸和甘油中的一种或其 中多种的组合。 5. The biodegradable material according to any one of claims 1 to 3, characterized in that: the plasticizer is one or more of sorbitol, polyethylene glycol, acetylated citric acid and glycerol. The combination.
6、根据权利要求 1一 3任一项所述的生物降解材料，其特征在于: 所述反应促进剂为偶联剂和催化剂中的一种或两者的组合。 6. The biodegradable material according to any one of claims 1 to 3, characterized in that: the reaction accelerator is one or a combination of a coupling agent and a catalyst.
7、 根据权利要求 6所述的生物降解材料， 其特征在于： 所述偶 联剂为 γ-氨丙基三乙氧基硅垸、二苯基甲垸二异氰酸酯和聚甲基对苯 异氰酸酯中的一种或者其中多种的组合。 7. The biodegradable material according to claim 6, characterized in that: the coupling agent is γ-aminopropyltriethoxysilane, diphenylmethane diisocyanate and polymethyl p-phenylene isocyanate. one or a combination of more than one of them.
8、 根据权利要求 6所述的生物降解材料， 其特征在于： 所述催 化剂为柠檬酸、己二酸、丁二酸和盐酸中的一种或者其中多种的组合。 8. The biodegradable material according to claim 6, characterized in that: the catalyst is one of citric acid, adipic acid, succinic acid and hydrochloric acid or a combination of more than one thereof.
9、 权利要求 1所述的生物降解材料的制备方法， 其特征在于包 括下述步骤： 将 3-羟基丁酸和 4-羟基丁酸共聚物、 聚丁二酸丁二醇 酯、聚乳酸、植物油、增塑剂和反应促进剂混合均匀，得到混合物料; 然后将混合物料加入到双螺杆挤出机中熔融共混， 形成物料熔体； 物 料熔体从双螺杆挤出机的模头挤出后进行拉条、切粒，得到物料颗粒； 物料颗粒经干燥处理后， 得到生物降解材料。 9. The method for preparing biodegradable materials according to claim 1, characterized by comprising the following steps: combining 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, polybutylene succinate, polylactic acid, Vegetable oil, plasticizer and reaction accelerator are mixed evenly to obtain a mixed material; then the mixed material is added to the twin-screw extruder for melting and blending to form a material melt; the material melt is extruded from the die head of the twin-screw extruder. After being discharged, it is stretched and cut into particles to obtain material particles; after the material particles are dried, biodegradable materials are obtained.
10、权利要求 1所述的生物降解材料在制备生物降解薄膜中的应 用， 将所述生物降解材料经单螺杆吹膜机吹膜， 得到生物降解薄膜。 10. The application of the biodegradable material of claim 1 in the preparation of biodegradable films, by blowing the biodegradable material through a single-screw film blowing machine to obtain a biodegradable film.
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