CN1164661C - Starch-based biodegradable material and its preparation method - Google Patents
Starch-based biodegradable material and its preparation method Download PDFInfo
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- CN1164661C CN1164661C CNB011382902A CN01138290A CN1164661C CN 1164661 C CN1164661 C CN 1164661C CN B011382902 A CNB011382902 A CN B011382902A CN 01138290 A CN01138290 A CN 01138290A CN 1164661 C CN1164661 C CN 1164661C
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- 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
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- 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
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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Abstract
The present invention discloses a starch-based complete biodegradable material and a preparation method thereof. The starch-based complete biodegradable material is prepared from the following components of the weight proportion: 65 to 95% of plant starch, 1 to 15% of reactive auxiliary agent and 1 to 30% of biodegradable high-molecular compound. The starch-based complete biodegradable material is prepared by the following steps: 1) the plant starch and the reactive auxiliary agent are added and mixed in a high speed mixer; 2) when the temperature is raised to 80 to 200 DEG C, the synthetic high-molecular compound can be degraded; 3) a powder material is obtained by temperature drop and discharging; 4) the powder material is added into a screw extruder, and the reactive auxiliary agent is added to the powder material at 120 to 230 DEG C; and thus, the starch-based complete biodegradable material is obtained by sheet extruding, pressing, polishing, cooling and forming. Two reaction processes of 'reactive plasticization' and 'reactive compatibilization' are simultaneously accomplished in special equipment, and the sheets having the thickness of 0.2 to 2.5 mm are directly extruded. The material solves the problem that the existing biodegradable materials have insufficient degradation, poor water resistance, oil resistance and weatherability and non ideal physical and chemical sanitary indexes and has the advantages of excellent flexibility and mechanical property, optimal water resistance, oil resistance and weatherability, no toxicity, no harm and complete biodegradation. Besides, the starch-based complete biodegradable material can be recycled as compost or a substrate for soil-less cultivation after being discarded, and thus, the starch-based complete biodegradable material belongs to the new environment protecting material with new and high science and technology. The starch-based complete biodegradable material can be used for producing disposable tableware.
Description
Technical Field
The invention relates to a degradable material and a preparation method thereof, in particular to a starch-based fully biodegradable material and a preparation method thereof.
Background
The development of green industry, the creation of green enterprises, the production of green products, the provision of green services and the advocation of green consumption are the main melodies of the twenty-first century. Population, resources and environment are three major problems faced by the sustainable development of the society at present, and the sustainable development of population,economy, society, environment and resources is realized, so that the sustainable development of the population, economy, society, environment and resources is the basic national policy of all countries in the world. In this context, "ecological materials" have come to bear. The 'ecological environment material' is a sixth generation material following human history 'natural material', 'metal material', 'synthetic material', 'composite material' and 'intelligent material', and belongs to a new environment-friendly material with high and new technology. On the basis of quantitatively and comprehensively analyzing and evaluating the environmental load of the material in the whole life cycle (raw material supply, raw material input, production process, output, use and abandonment … …) from the design stage of the material, the negative influence on resources and the environment is fully considered to be reduced as much as possible, and the problems of increasing shortage of resources, increasing deterioration of ecological environment caused by a large amount of wastes and the like are fundamentally solved.
In order to treat the white pollution, some research institutions at home and abroad are devoted to research and development of starch filled type optical/biological dual-degradable plastics and products from the late eighties, and the research and development of the disposable degradable materials show colorful and colorful glaring scenes.
The inventor with publication number CN1296997A adopts plant fiber powder, polyvinyl alcohol, carboxymethyl cellulose, stearic acid and flour, which are mixed with water and molded under lower pressure, wherein the polyvinyl alcohol and the flour are used as a binder; carboxymethyl cellulose plays a role in toughening and reinforcing, and the carboxymethyl cellulose has the advantages of higher fiber content, higher prices of polyvinyl alcohol and carboxymethyl cellulose, and high energy consumption and low efficiency because the production mode adopts mould pressing. In addition, it must be emphasized that since the above-mentioned products are not water-proof and oil-proof, the inner surface of the products must be coated with waterproof glue or polyethylene film, otherwise the physical and chemical hygienic indexes are not up to the standard. The product has higher cost and is not easy to be accepted by the market.
There is a "light/biodegradable material" which is made by filling polyethylene polypropylene with powdered ore (talc powder, calcium carbonate) or a small amount of starch and molding on conventional plastic processing equipment, and there is no patent disclosure so far. From the analysis of the products on the market, there are two process routes: 1. adding the light-biodegradable plastic master batch filled with starch or mineral powder into polyethylene according to a certain proportion, generally not more than 50%, uniformly mixing, adding into a single-screw extruder, extruding through a sheet extrusion die head, and directly performing vacuum plastic-suction molding on extruded sheets on a rotary molding machine; low production efficiency, low finished product rate, soft product, low strength and no practical use value. 2. Adding the light-biodegradable plastic master batch filled with starch or mineral powder into polyethylene or polypropylene according to a certain proportion, generally not more than 50%, uniformly mixing, adding into a single-screw extrusion sheet machine set, and calendering by three rollers to obtain a sheet. Some of the products have substandard performance, and some of the products have low starch content and can only be partially degraded.
The main reasons for analyzing the low starch content of the existing product are formula, process and equipment limitation.
The patent inventors with publication numbers of CN1115771A, CN1289792A, CN1280246A, etc. firstly pretreat starch to prepare modified starch, and plasticize with polyhydric alcohol; modified starch PE, photosensitizer, oxidizing promoter, degradation promoter, autoxidant, coupling agent or ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer compatilizer, etc. are mixed in high mixing, and the mixture is extruded and granulated by double screws to prepare the master batch containing at least 30-50% of starch. The coupling agent is mostly titanate coupling agent or aluminate coupling agent, and the ethylene-acrylic acid copolymer and ethylene-vinyl acetate copolymer have high market price, which leads to high production cost. The use of a photosensitizer, which is an organic compound of a transition metal, indicates that the master batch and the product disclosed in the above patent have poor degradation performance, and the photosensitizer is needed, and in addition, the addition of the photosensitizer pollutes the product. In the compositions disclosed in the above patents, polyolefin is still used as the main raw material, and starch is merely filled therein as a biodegradation agent, and the product is still not completely degraded.
The composition disclosed in the publication No. CN1288100A is added with 40-80% of graft modified starch copolymer, photosensitizer, plastic additive, muscovite powder, etc. The same CN1319618A also discloses a method for copolymerization of starch derivatives/cellulose/acrylic acid. Generally speaking, the starch is modified by graft copolymerization with ethylenically unsaturated monomers under the action of free radical initiators. The graft copolymerization of starch is completed in a reactor outside a double-screw machine, the reaction efficiency is low, the production cost is high, and the starch is not economical as a raw material of disposable products.
Disclosure of Invention
The invention aims to provide a starch-based fully biodegradable material which has excellent flexibility and mechanical properties, excellent water resistance, oil resistance and weather resistance and can be completely biodegraded, aiming at the defects that the product cannot be completely degraded, the material is poor in water resistance, oil resistance and weather resistance and the physicochemical hygienic indexes are not ideal, so as to make up for the defects of the product.
The invention also aims to provide a preparation method of the starch-based fully biodegradable material.
The starch-based fully biodegradable material consists of plant starch, a reactive plasticizer, a reactive compatibilizer and a biodegradable high molecular compound, and the weight ratio is as follows:
65-95% of plant starch;
1-15% of reactive auxiliary agent;
1-30% of biodegradable high molecular compound;
the reactive auxiliary agent comprises a reactive plasticizer and a reactive compatibilizer, the reactive plasticizer is one or more of aliphatic carboxylic acid, aliphatic amide, aliphatic carboxylic acid metal salt, low molecular polyolefin and phenolic antioxidant, and the reactive compatibilizer is one or more of comonomer, anhydride and derivative.
The plant starch used in the invention is potato starch and grain starch, and specifically is one or more of sweet potato starch, cassava starch, konjac starch, corn starch, wheat flour and early rice starch.
The biodegradable high molecular compound used in the invention is one or more of poly (ethyl propyl acetate), polylactide, polylactic acid, poly (hydroxybutyrate-valerate) copolymer, polyvinyl alcohol and aliphatic polyester-polyamide copolymer. The main function is to chemically combine with starch to play the roles of strengthening, toughening and plasticizing.
The reactive plasticizer used in the invention is one or more of aliphatic carboxylic acid, aliphatic amide, aliphatic carboxylic acid metal salt, low molecular polyolefin and phenolic antioxidant, and the reactive compatibilizer is one or more of comonomer, acid anhydride and derivative. In the reaction system disclosed by the invention, the selected auxiliary agent shows high reaction efficiency, mild reaction conditions and stable operation in a special double-screw extrusion sheet machine set, and each auxiliary agent plays multiple roles.
The aliphatic carboxylic acid is one or more of oleic acid, linoleic acid, stearic acid, palmitic acid, lauric acid, myristic acid, linolenic acid, succinic acid, and malic acid.
The aliphatic amide is one or more of oleamide, stearamide, linoleamide, naphthenic amide, caprolactam and laurolactam.
The metal salt of aliphatic carboxylic acid is one or more of manganese oleate, ferrous oleate, magnesium stearate, ferrous stearate, calcium stearate, zinc stearate, and manganese stearate.
The comonomer is one or more of acrylonitrile, vinyl acetate, acrylamide, isoprene, acrylic acid, alkyl methacrylate and styrene.
The anhydride and derivatives are one or more of acetic anhydride, methacrylic anhydride, succinic anhydride, maleic anhydride, and maleimide.
The low molecular polyolefin is one or more of paraffin, polyethylene wax, polypropylene wax and liquid paraffin.
The phenolic antioxidant is specifically 2, 6-di-tert-butyl-4-cresol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate].
The most prominent characteristics of the invention are as follows: the conversion of starch into thermoplastic material is achieved by a 'reactive plasticization' mechanism. In principle, a certain amount of micromolecular polar compounds are added into starch to play a plasticizing role, and in the prior art, a certain amount of micromolecular polar compounds are added into starch. The inventor realizes two-step reaction in a special double-screw extruder:
esterification reaction of aliphatic carboxylic acid and starch
The plasticizing effect has three characteristics: 1. high reaction efficiency, 2, small dosage of the auxiliary agent, 3, good plasticizing effect, and the excessive auxiliary agent can simultaneously play the roles of a lubricant, a self-oxidant and a degradation promoter.
Secondly, graft copolymerization of starch and graft monomer
The general method for realizing starch thermoplastic transformation by starch graft copolymerization comprises three types: 1. free radical initiation, 2, ionic interaction, 3, ozone. The inventor adopts another brand-new method: i.e. first a complex of the grafting monomer with the anhydride and its derivatives is prepared. For example styrene and maleic anhydride
Thereby reducing the activation energy of the double bonds, generating the state of coexistence of ionic state and free radical under the action of high temperature and shearing force of a special double-screw extruder, and realizing the graft copolymerization modification of the starch.
And
the product is a very ideal compatilizer of starch and biodegradable high molecular compound.
The preparation method comprises the following steps:
1) adding the plant starch and a part of the reactive plasticizer into a special high-speed mixer for mixing.
2) Adding biodegradable high molecular compound when the temperature is increased to 80-130 deg.C
3) Cooling and discharging to obtain powder
4) Adding the powder into a screw extruder, adding a part of reactive compatibilizer at the temperature of 120-230 ℃, extruding the sheet, and performing calendaring, cooling, sizing and rolling to obtain the finished product.
The invention has excellent flexibility and mechanical property, folding resistance, falling resistance, impact resistance and the like; the water resistance and the oil resistance are excellent, and no paint or polyethylene film is coated on the surface; the high temperature resistance and the low temperature resistance are outstanding, and the product can be used in refrigerators and microwave ovens; no toxicity and harm and complete use; can be completely biodegraded. Under normal climatic conditions, the fertilizer becomes powder in a high-temperature composting environment for half a month, and after three months, the fertilizer is detected to be completely converted into small molecular polar compounds such as carboxylic acid, ketone compounds, aldehyde compounds, nitrogen-containing compounds and the like except for releasing a certain amount of carbon dioxide due to microbial metabolism, so that the fertilizer is harmless and beneficial to the environment. Practice proves that the starch-based fully biodegradable material and the product are recycled after being discarded, can be composted or used as a soilless culture substrate, completely realize virtuous circle, and belong to ecological environment materials.
The preparation method of the invention realizes the graft copolymerization of starch and graft monomer under the condition of no free radical initiation by the action of reactive plasticizer and compatibilizer in a special meshed parallel co-rotating twin-screw extrusion sheet machine set, simplifies the process, has no pollution in production and reduces the production cost.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example one, weigh 100 mesh corn starch 38Kg, konjaku starch 2Kg, paraffin 1.84Kg, add into the specialized high-speed mixer preheated to 70 deg.C sequentially, start and stir, add oleic acid 0.12Kg, stearic acid 0.12Kg, zinc stearate 0.34g, oleamide 0.53Kg, tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]pentaerythritol ester 0.02Kg sequentially, continue to stir, when the temperature of the supplies in the mixer rises to 110 deg.C, add polycaprolactone 10Kg, discharge to the low-speed cooling mixer, stir at low speed, cool, dehumidify, discharge, pack;
the powder is added into a meshing parallel co-rotating twin-screw extrusion sheet machine at the temperature of 185-190 ℃, the die head temperature of 160 ℃, the screw rotating speed of 300rpm, and simultaneously 0.74Kg of dehydrated malic acid and polyethylene composition is uniformly injected into a second section of liquid feed inlet. Extruding the sheet, calendering, cooling, sizing and rolling by a three-roller calender to obtain the sheet with the thickness of 0.2-2.5mm, white, fine and glossy.
Example two: weighing 40Kg of cassava starch with 100 meshes and 1.82Kg of paraffin, putting the cassava starch and the paraffin into a special heating high-speed mixer preheated to 70 ℃, starting up the mixer for stirring, sequentially adding 0.52Kg of adipic acid, 0.42Kg of stearic acid, 0.85Kg of caprolactam, 0.13Kg of calcium stearate and 0.05Kg of 2, 6-di-tert-butyl-4-cresol for continuous stirring, adding 8Kg of polylactic acid when the temperature of materials in the mixer rises to 120 ℃, discharging the materials in a low-speed cooling mixer, stirring at low speed, cooling, dehumidifying, discharging and packaging.
Adding the powder into a meshing parallel co-rotating twin-screw sheet extrusion unit, wherein the temperature is 165-.
Example three, take 100 mesh early rice starch 40Kg, swell polyvinyl alcohol 2Kg, paraffin 1.32Kg with hot water, put into the specialized high-speed mixer preheated to 70 ℃, start the stirring, add stearic acid 0.20Kg, zinc stearate 0.12Kg, calcium stearate 0.65Kg, oleic acid 0.05Kg, oleamide 0.50Kg, 2, 6-di-tert-butyl-4-cresol 0.02Kg sequentially and continue to stir when the temperature of the supplies in the mixer rises to 110 ℃, discharge to the low-speed cooling mixer, stir at low speed, cool, dehumidify, discharge, pack.
Adding the powder into a special double-screw extrusion sheet machine set, wherein the temperature of a die head is 165-175 ℃, the rotation speed of a screw is 300rpm, simultaneously, uniformly injecting 1.20Kg of acrylamide into a second section liquid feed inlet, extruding the sheet, and performing calendaring, cooling, sizing and rolling by a three-roll calendar to obtain the sheet with the thickness of 0.2-2.5mm, and the color is white and glossy.
Example four, weighing 48Kg of 100 mesh corn starch, 4Kg of fattyacid polyester/polyamide copolymer and 2Kg of paraffin, putting the weighed materials into a special high-speed mixer preheated to 70 ℃, continuously stirring, sequentially adding 0.18Kg of salicylic acid, 0.25Kg of malic acid, 0.50Kg of stearic acid, 0.52Kg of linoleamide, 0.10Kg of stearamide, 0.12g of zinc stearate and 0.16Kg of tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]pentaerythritol ester, continuously stirring, discharging the materials in the mixer to 110 ℃, discharging the materials into a low-speed cooling stirrer, cooling, dehumidifying, discharging and packaging.
Example five, take 100 mesh starch 48Kg, konjaku starch 2Kg, polyethylene wax 2Kg, paraffin 1.2Kg, add into the specialized high-speed mixer preheated to 70-80 deg.C sequentially, start the stirring, add 0.71Kg of laurolactam, 0.12Kg of oleamide, 0.27Kg of zinc stearate, 0.53Kg of malic acid sequentially, continue stirring, when the temperature of the materials in the mixer rises to 100 plus 120 deg.C, discharge to the low-speed cooling mixer, stir at low speed, cool, dehumidify, discharge, pack.
Adding the powder into a meshed parallel co-rotating twin-screw extrusion sheet machine set, wherein the temperature is 165 plus one year, the die head temperature is 135 ℃, the screw rotating speed is 360rpm, meanwhile, 0.73Kg of styrene is uniformly injected into a second section liquid feeding port, and the extruded sheet is subjected to calendaring, cooling, sizing and rolling by a three-roller calendaring machine to obtain a sheet with the thickness of 0.2-2.5mm, and the sheet is white and glossy.
In the sixth embodiment, 30Kg of corn starch of 100 meshes, 5Kg of early rice starch, 0.5Kg of paraffin, 1.0Kg of polypropylene wax, 0.42Kg of succinic acid, 0.13Kg of malic acid, magnesium stearate and 1.12Kg of calcium stearate composition are sequentially added into a special high-speed mixer preheated to 70-80 ℃, 15Kg of poly (hydroxybutyrate-valerate) copolymer is added when the temperature of the materials rises to 130 ℃, the materials are uniformly mixed and discharged into a low-speed cooling stirring mixer, and the materials are stirred, cooled, dehumidified, discharged and packaged at low speed;
adding the powder into a special double-screw extrusion sheet machine set, wherein the temperature is 185 ℃ for 160 ℃ for one time, the temperature of a die head is 135 ℃ for one time, the rotating speed of the screw is 420rpm, simultaneously, 0.64Kg of propylmethyl propylbenzene propionate is uniformly injected into a second-stage liquid feeding port, extruding the sheet, and obtaining the sheet with the thickness of 0.20-2.5mm through a three-roller calender, calendering, cooling, sizing and rolling, wherein the sheet is yellowish and glossy;
the seventh embodiment is that 100 mesh wheat flour 40Kg, konjac starch 2.0Kg, paraffin 0.52Kg, polypropylene wax 1.20Kg are taken and added into a special high speed mixer preheated to 70-80 ℃, and are continuously stirred, oleic acid and lauric acid composition 0.81Kg, zinc stearate and calcium stearate composition 0.62Kg are sequentially added, when the temperature of the materials is raised to 110-120 ℃, the materials are discharged into a low speed cooling mixer, and are stirred at low speed, cooled, dehumidified, discharged and packaged.
Adding the materials into a special double-screw extrusion sheet machine set, wherein the temperature is 155 ℃ for 130 plus materials, the temperature of a die head is 120 plus materials, the rotating speed of the screw is 190rpm for 170 plus materials, uniformly injecting 1.62Kg of the vinyl acetate and malic acid dehydrate composition into a second-stage liquid feed inlet, extruding the sheet, and obtaining the sheet with the thickness of 0.2-2.5mm through a three-roller calender, calendaring, cooling, sizing and rolling, and the sheet is yellowish and glossy.
The invention has multiple uses
(1) Continuously vacuum-forming the sheet material into various specifications of lunch boxes with flip covers and various shapes of plates, boxes, plates and the like by a special negative pressure thermoforming machine;
(2) the sheet material of the invention is continuously molded into cups, boxes, bowls, barrels (for fast food noodles) and the like with various specifications and shapes by a special positive pressure thermoforming machine;
(3) the leftover material, leftover material and defective product of the invention can be recycled for a plurality of times and can be processed into products without changing color and performance.
(4) The invention can also be made into various packaging containers and shock-absorbing fillers.
The product of the invention is tested by the national plastic product quality supervision and inspection center and the safety and health inspection station of the product quality supervision and inspection center of Ministry of railways, the physical and chemical health indexes, the use performance and the biodegradation performance of the product all meet the technical requirements of the national standard GB18006.1-1999 on edible starch products, and the cost is obviously lower than similar products at home and abroad.
In order to prevent the counterfeit products from counterfeiting the products of the invention, the invention discloses a method for identifying the authenticity, which is intuitive, convenient, quick, accurate and reliable: when the product of the invention is ignited, no molten material drips off, and the product turns into white or gray ash after complete combustion. The fake and inferior product is prepared by filling polyolefin as main material with small amount of starch, mineral powder or color concentrate, and when ignited, the product has molten matter dripping, black smoke, bad smell and flame extinguished to form hard black plastic block.
Claims (12)
1. A starch-based fully biodegradable material comprises plant starch, a reaction type auxiliary agent and a biodegradable high molecular compound, and the weight ratio is as follows:
65-95% of plant starch;
1-15% of reactive auxiliary agent;
1-30% of biodegradable high molecular compound;
the reactive auxiliary agent comprises a reactive plasticizer and a reactive compatibilizer, the reactive plasticizer is one or more of aliphatic carboxylic acid, aliphatic amide, aliphatic carboxylic acid metal salt, low molecular polyolefin and phenolic antioxidant, and the reactive compatibilizer is one or more of comonomer, anhydride and derivative.
2. A starch-based fully biodegradable material according to claim 1, characterized in that: the plant starch is one or more of sweet potato starch, tapioca starch, rhizoma Amorphophalli starch, corn starch, wheat flour, and early rice starch.
3. A starch-based fully biodegradable material according to claim 1, characterized in that: the biodegradable high molecular compound is one or more of poly (ethyl propyl acetate), poly (lactide), poly (lactic acid), poly (hydroxybutyrate-valerate) copolymer, polyvinyl alcohol and aliphatic polyester-polyamide copolymer.
4. A starch-based fully biodegradable material according to claim 1, characterized in that: the aliphatic carboxylic acid is one or more of oleic acid, linoleic acid, stearic acid, palmitic acid, lauric acid, myristic acid, linolenic acid, succinic acid and malic acid.
5. A starch-based fully biodegradable material according to claim 1, characterized in that: the aliphatic amide is one or more of oleamide, stearamide, linoleamide, naphthenic amide, caprolactam and laurolactam.
6. A starch-based fully biodegradable material according to claim 1, characterized in that: the metal salt of aliphatic carboxylic acid is one or more of manganese oleate, ferrous oleate, magnesium stearate, ferrous stearate, calcium stearate, zinc stearate and manganese stearate.
7. A starch-based fully biodegradable material according to claim 1, characterized in that: the comonomer is one or more of acrylonitrile, vinyl acetate, acrylamide, isoprene, acrylic acid, alkyl methacrylate and styrene.
8. A starch-based fully biodegradable material according to claim 1, characterized in that: the anhydride and the derivative are one or more of acetic anhydride, methacrylic anhydride, succinic anhydride, maleic anhydride and maleimide.
9. A starch-based fully biodegradable material according to claim 1, characterized in that: the low molecular polyolefin is one or more of paraffin wax, polyethylene wax, polypropylene wax and liquid paraffin.
10. A starch-based fully biodegradable material according to claim 1, characterized in that: the phenolic antioxidant is 2, 6-di-tert-butyl-4-cresol, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate].
11. The method for preparing the starch-based fully biodegradable material of claim 1, which comprises the following steps:
1) adding plant starch and reactive plasticizer into a high-speed mixer for mixing
2) Adding biodegradable high molecular compound when the temperature is increased to 80-130 deg.C
3) Cooling and discharging to obtain powder
4) Adding the powder into a screw extruder, adding a reactive compatibilizer at the temperature of 120-230 ℃, extruding a sheet, and performing calendaring, cooling and shaping.
12. Use of a starch-based fully biodegradable material according to claim 1, characterized in that: it can be used to make disposable tableware, packing container and damping filler.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011382902A CN1164661C (en) | 2001-12-17 | 2001-12-17 | Starch-based biodegradable material and its preparation method |
| PCT/CN2002/000810 WO2003051981A1 (en) | 2001-12-17 | 2002-11-15 | Starch-based fully-biodegradable materials and their preparation process |
| AU2002366251A AU2002366251A1 (en) | 2001-12-17 | 2002-11-15 | Starch-based fully-biodegradable materials and their preparation process |
| KR10-2003-7013194A KR20040078043A (en) | 2001-12-17 | 2002-11-15 | Starch-based fully-biodegradable materials and their preparation process |
| TW092106515A TW593514B (en) | 2001-12-17 | 2003-03-24 | Starch-based fully-biodegradable material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011382902A CN1164661C (en) | 2001-12-17 | 2001-12-17 | Starch-based biodegradable material and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1354196A CN1354196A (en) | 2002-06-19 |
| CN1164661C true CN1164661C (en) | 2004-09-01 |
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| CNB011382902A Expired - Lifetime CN1164661C (en) | 2001-12-17 | 2001-12-17 | Starch-based biodegradable material and its preparation method |
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| Country | Link |
|---|---|
| KR (1) | KR20040078043A (en) |
| CN (1) | CN1164661C (en) |
| AU (1) | AU2002366251A1 (en) |
| TW (1) | TW593514B (en) |
| WO (1) | WO2003051981A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112779792A (en) * | 2020-12-24 | 2021-05-11 | 苏州市和好塑业有限公司 | Degradable snack box packing material and its making process |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1006077A3 (en) * | 1992-07-15 | 1994-05-10 | Solvay | Biodegradable molding compositions including at least one thermoplastic starch and at least one thermoplastic aliphatic polyester. |
| US5910520A (en) * | 1993-01-15 | 1999-06-08 | Mcneil-Ppc, Inc. | Melt processable biodegradable compositions and articles made therefrom |
| JP4241930B2 (en) * | 1996-08-09 | 2009-03-18 | ビオ−テック ビオロギッシェ ナトゥーアフェアパックンゲン ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Thermoplastically processable starch or starch derivative-polymer mixture |
| EP0950689B1 (en) * | 1996-11-05 | 2004-10-06 | NOVAMONT S.p.A. | Biodegradable polymeric compositions comprising starch and a thermoplastic polymer |
-
2001
- 2001-12-17 CN CNB011382902A patent/CN1164661C/en not_active Expired - Lifetime
-
2002
- 2002-11-15 WO PCT/CN2002/000810 patent/WO2003051981A1/en not_active Application Discontinuation
- 2002-11-15 KR KR10-2003-7013194A patent/KR20040078043A/en not_active Application Discontinuation
- 2002-11-15 AU AU2002366251A patent/AU2002366251A1/en not_active Abandoned
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2003
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112779792A (en) * | 2020-12-24 | 2021-05-11 | 苏州市和好塑业有限公司 | Degradable snack box packing material and its making process |
| RU2796732C1 (en) * | 2022-08-01 | 2023-05-29 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" | Composition for producing biodegradable polymer material and biodegradable polymer material on its basis |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002366251A1 (en) | 2003-06-30 |
| TW593514B (en) | 2004-06-21 |
| WO2003051981A1 (en) | 2003-06-26 |
| KR20040078043A (en) | 2004-09-08 |
| TW200418918A (en) | 2004-10-01 |
| CN1354196A (en) | 2002-06-19 |
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