TW593514B - Starch-based fully-biodegradable material and its preparation method - Google Patents

Abstract

The present invention relates to a starch-based fully-biodegradable material which comprises 65-95 wt% plant starch, 1-15 wt% reactive plasticizer, 0.1-5 wt% reactive compatibilizer, and 1-20wt% biodegradable polymer. The preparation process of the starch-based fully-biodegradable material is as follows: (1) adding the plant starch and the reactive plasticizer to a high speed mixer to mix; (2) when its temperature rises to 80-200 DEG C, adding the degradable polymer thereto; (3) cooling and discharging to obtain powder material; (4) then adding the powder to a twin screw extruder, adding the reactive compatibilizer thereto at 120-130 DEG C, and extruding this sheet, polishing, cooling and sizing, thereby completing the invention. After discarding, the fully-biodegradable material according to the invention can be composted or used as mediums for soil-less culture. It can be used to manufacture disposable tableware, packing container and vibration-damping filler and the like.

Description

(1) 发明. Description of the invention The technical field to which the invention belongs The present invention relates to a crude material of degraded material, its shaking, and a method for preparing the same, in particular to a starch-based biodegradable material and a method for preparing the same. [Previous technology] "Developing a green industry ', setting up four green enterprises, producing green products, providing green services, and advocating green elimination" ^ κ is the main theme of the 21st century. Population, resources, and environment are the three major issues facing today's sustainable development. Realizing the sustainable development of population, economy, society, economics, and resources has become a basic concern of the world. Under the background, "ecological environment materials" came into being. "Eco-environmental materials are sixth-generation materials after human history ±" natural materials "," metal materials "," synthetic materials ", and" smart materials ", which belong to high-tech environmental protection new materials. From the design stage of the material, it quantitatively comprehensively analyzes and evaluates the material on the basis of the environmental load in its entire search cycle (raw material supply-raw material input-production process-output-use-waste), and fully considers reducing the sealing resources as much as possible. The negative impact of each environment. Fundamentally solve the problems of increasingly scarce resources, and the deterioration of the ecological environment caused by a large amount of waste. To combat "white pollution" 'From the late 1980s, some domestic and foreign research institutions committed to starch. The research and development of filled photo / biologically degradable materials and products, and the research and development of disposable degradable materials present a colorful and pleasing scene. The patent application published as CN 1 2966997A uses plant fiber powder-6- (2 ), Polyvinyl alcohol, carboxymethylcellulose, stearic acid and flour after mixing with water, forming under lower pressure, where Vinyl alcohol, flour is used as a binder; carboxymethyl cellulose has a toughening and strengthening effect. However, in this method, polyvinyl alcohol and carboxymethyl cellulose are relatively expensive, and the production method uses molding, with high energy consumption and low efficiency. In addition, It must be emphasized that because the above products are not resistant to water and oil, they need to be coated with waterproof glue or polyethylene film on the inner surface, otherwise the physical and chemical hygiene indicators are not up to the standard. The above products are relatively expensive and are not easily accepted by the market. "Photo / biodegradable material", which is filled with mineral powder (talc, calcium carbonate) or a small amount of starch in polyethylene or polypropylene. It is molded on traditional plastic processing equipment. No patent application has been seen so far. From the analysis of the products on the market, there are two kinds of process routes: 1. Add the photo-biodegradable plastic masterbatch filled with starch or mineral powder to polyethylene in a certain proportion, generally not more than 50% by weight, and add it after mixing. The single screw extruder extrudes the sheet through the sheet extrusion die, and performs vacuum suction molding directly on the crawler molding machine. This method has low production efficiency, low yield and low yield. The resulting product is very soft, low in strength, and has no actual price. 2. Add the photo-biodegradable plastic masterbatch filled with starch or mineral powder to polyethylene or polypropylene in a certain proportion, generally not more than 50% by weight. After mixing, it is added to the single-screw extruding sheet unit to form a sheet through three-roll calendering. The starch content of the above products is low and can only be partially degraded. The main reasons for the low starch content of the existing products are analyzed. The second is technology and the third is equipment.

Patent applications with publication numbers CN 1 1 1 577 1 A, CN 1 289792A, and CN 1 280246A disclose the following method: First, the starch is subjected to -7- (3) 593514

Pre-treatment to make modified starch and plasticize it with polyalcohol; modified starch, PE, photosensitizer, pro-oxidant, degradation promoter, auto-oxidant, coupling agent or ethylene-acrylic acid copolymer, ethylene · vinyl acetate The copolymer compatibilizer is mixed in a high-speed mixer, and twin-screw extrusion granulation is made into a masterbatch containing 30-85% starch. Among these coupling agents, titanate coupling agents or aluminate coupling agents are mostly used. Due to the high market prices of ethylene-acrylic acid copolymers and ethylene-vinyl acetate copolymers, production costs remain high. The above method also uses a transition metal organic compound photosensitizer, which indicates that the masterbatch and products disclosed in the above patents have poor degradation performance, and the use of a photosensitizer is required. In addition, the addition of the photosensitizer also contaminates the product. In the composition disclosed in the above patent application, polyolefin is still used as the main raw material, starch is only used as a carbon source for microorganisms, and the product still cannot be completely degraded.

The composition disclosed in the patent application with publication number CN 1 288 1 00A is added with 40 to 80% of graft-modified starch copolymer, photosensitizer, plastic additive, muscovite powder, and the like. CN 13 1961 8A also discloses a method using a starch derivative / cellulose / acrylic acid copolymer. In general, starch is modified by graft copolymerization with ethylenically unsaturated monomers under the action of a free radical initiator. The graft copolymerization of starch is completed in a reactor other than the twin screw machine. The reaction efficiency is low, the production cost is high, and it is not cost-effective as a raw material for disposable products. [Summary of the Invention] The purpose of the present invention is to address the defects that the above products cannot be completely degraded, the materials are water-resistant, oil-resistant, weather-resistant, and the physical and chemical health indicators are unsatisfactory. -8-(4) (4) 593514 It has excellent water resistance, oil resistance and weather resistance. It is a starch-based biodegradable material that can completely biodegrade to make up for the shortcomings of the above products. Another object of the present invention is to provide a method for preparing the starch-based biodegradable material. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a starch-based biodegradable material, which includes the following components: 65-95% by weight of plant starch, 1- 15% by weight of a reactive plasticizer, and the reactive plasticizer is selected 0.1-5% by weight selected from a molar ratio of 1: 1 from one or more of an aliphatic carboxylic acid, an aliphatic low-molecular polyester, an aliphatic ammonium amine, an aliphatic carboxylic acid ester, and an aliphatic carboxylic acid metal salt. Reactive compatibilizer of a complex of a comonomer with an acid anhydride or a derivative thereof, wherein the comonomer is selected from the group consisting of acrylonitrile, vinyl acetate, acrylamide, isoprene, acrylic acid, and methacrylic acid alkyl One or more of an ester and styrene; the anhydride or derivative thereof is one or more selected from the group consisting of acetic anhydride, methylpropionic anhydride, succinic anhydride, maleic anhydride, and maleimide, and 1-20 Biodegradable polymer compound in weight%, said biodegradable polymer compound is selected from the group consisting of polycaprolactone, polyethylene glycol, polylactide, polylactic acid, polyhydroxybutyrate and valerate Copolymer, polyvinyl alcohol, polyacetic acid Enester - polyacrylamide copolymer, and a reaction type compatibilizing agent of the modified polyethylene and polypropylene, one or more of. -9- (5) (5) 593514 The plant starch used in the present invention is selected from potato starch '_ 彳 Wuyuan powder, specifically sweet potato starch, potato starch, cassava starch, konjac starch, corn starch, wheat flour and One or more of early rice starch. The main function of the biodegradable polymer compound used in the present invention is to chemically combine with starch to produce strengthening, toughening, and plasticizing effects. 0 Aliphatic carboxylic acid used as a reactive plasticizer in the present invention Is one selected from the group consisting of oleic acid, linoleic acid, stearic acid, palmitic acid, adipic acid, lauric acid, myristic acid, linolenic acid, succinic acid, malic acid, acetic acid, and flea acid Multiple. The aliphatic ammonium used as a reactive plasticizer in the present invention is selected from the group consisting of oleylamine, stearylamine, linoleylamine, naphthylamine, caprolactam, dodecylamine, N One or more of N-dibutylstearylamine and N, N-dimethyloleylamine. The metal salt of an aliphatic carboxylic acid used as a reactive plasticizer in the present invention is selected from the group consisting of manganese oleate, ferrous oleate, magnesium stearate, ferrous stearate, calcium stearate, and stearic acid. One or more of zinc, manganese stearate and zinc pyrrolidone stearate. The aliphatic carboxylic acid ester used as the reactive plasticizer in the present invention is selected from the group consisting of methoxyethyl oleate, diisooctyl sebacate, dibutoxyethyl adipate, and dibenzyl sebacate One or more of esters, isooctyl isodecyl nylon acid butyl epoxide oleate, butyl ricinoleate ricinoleate, and unblocked propylene glycol adipate polyester having a molecular weight of 300-1,200. The biodegradable material of the present invention may further contain 0.1 to 3% by weight of -10-(6) (6) 593514 one or more kinds of physical additives selected from the group consisting of paraffin wax, polyethylene wax, polypropylene wax and liquid stone goblin. Plasticizer. The biodegradable material of the present invention may further contain a material selected from the group consisting of 2.6-di-dibutyl-4-cresol (264 antioxidant), 1,1,3-tris (2-methyl-4-hydroxy-5) -Antioxidants of second butylphenyl) butane (1010 antioxidant) and tetrakis [3- (3,5-disecond butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester. The most prominent feature of the present invention is that the "reactive plasticizing" mechanism is adopted to realize the transformation of starch into a thermoplastic material. In principle, adding a certain amount of small molecule polar compounds to starch has a plasticizing effect on starch. In the prior art, a certain amount of small molecule polar compounds are added to starch. The present invention realizes a two-step reaction in a twin-screw extruder: 1. The plasticization reaction of starch with a reactive plasticizer, such as:

St-〇H + H〇〇CR— St-〇〇CR + H2〇 This plasticizing effect has three major characteristics: 1, high reaction efficiency, 2, small amount of additives, 3, good plasticizing effect; excessive plasticization Agents can simultaneously act as lubricants, auto-oxidants, and degradation promoters. Compatibilization reaction of starch and reactive compatibilizer Compatibilization modification can be achieved by graft copolymerization of starch and comonomer. Generally there are three types of starch graft copolymerization methods: 1. free radical initiation method, 2. 00C0 radiation method, 3. ozone effect method. The present invention adopts another novel method -11-(7) 593514: firstly, a complex of a graft monomer, an acid anhydride and a derivative thereof is prepared. For example, the compound of styrene and maleic anhydride:

By the compound reaction not shown in the above formula, the activation energy of the double bond is reduced, and under the action of the temperature and shear force of the twin-screw extruder, ions and radicals coexist, resulting in the graft copolymerization of starch. :

CH = CH

V I

OH R—C — R ·

: C χ = ο Ο

O — fll Another reaction product is:

OH -12- (8) These products are ideal compatibilizers of starch and biodegradable polymer compounds. The present invention also provides a method for preparing the above starch-based biodegradable material. The method includes the following steps: 1) adding plant starch and the reactive plasticizer to a high-speed mixer for mixing, and 2) when the temperature rises to At 80-200 ° C, add the biodegradable polymer compound, 3) reduce the temperature to obtain the powder, 4) add the above powder to the twin-screw extruder, and add the Reactive compatibilizer, extruded sheet, completed by calendering, cooling, shaping, and rolling. The bio-degradable material of the present invention has excellent flexibility and mechanical properties' resistance to folding, drop resistance and impact resistance, etc. ; Excellent water and oil resistance; no surface coating or polyethylene film required; outstanding high temperature and low temperature resistance; can be used in refrigerators and microwave ovens; non-toxic and harmless, safe to use; fully biodegradable. Under normal climate conditions In the high-temperature compost environment, it became powdery for half a month. After three months, it was tested. Except for the release of a certain amount of carbon dioxide and water due to microbial metabolism, all of them turned into small molecule polar compounds. 'Such as carboxylic acid, ketone compounds, acid compounds, nitrogen-containing compounds, etc., are harmless to the environment and beneficial. When implemented, the starch-based biodegradable materials and products of the present invention are recovered after being discarded and can be composted or used. As a soilless cultivation substrate, a benign loop is fully realized, belonging to "Eco-Environmental Materials • 13-593514 〇) The manufacturing method of the present invention is to use a reactive plasticizer in a meshing parallel co-rotating twin-screw extrusion sheet unit And compatibilizer, in the absence of free radical initiation, to achieve the graft copolymerization of starch and grafting monomers, simplifying the process, production without pollution, and reducing production costs.

The following further describes the present invention with reference to the embodiments, but does not limit the scope of the present invention. Example 1

Weigh 38 kg of 100-mesh corn starch, 2 kg of konjac starch, and 1.84 kg of paraffin 'sequentially added to a high-speed mixer that has been preheated to 70, start up and stir' and then add 0.12 kg of oleic acid and 0.12 kg of stearic acid , 0.34 kg of zinc stearate, 0.53 kg of oleamide and 0.02 kg of 1010 antioxidant, continue to stir, and when the temperature of the material in the mixer rises to 1 丨, add 10 kg of polycaprolactone and discharge to a low speed Cooling in the mixer, stirring at low speed, cooling, dehumidifying, discharging, packaging. Add the above powder to the intermeshing parallel co-rotating twin-screw extrusion sheet unit. The barrel temperature is 1 85 — 1 90 ° C, the die temperature is 160 ° C, and the screw speed is 300 rpm. A 1: 1 composite of maleic anhydride and styrene. The extruded sheet is calendered, cooled, shaped, and rolled by a three-roll calender to produce a sheet with a thickness of 0.2 to 2.5 mm, which is white, delicate, and shiny. -14- (10) (10) 593514 Example 2 Weigh 40 kg of 100 mesh cassava starch and 1.82 kg of stone concrete, put it into a heating high-speed mixer that has been preheated to 70 ° C, start up and stir, and add 0.5 in turn. 2 kg of adipic acid, 0.42 kg of stearic acid, 0.85 kg of caprylamine, 0.13 kg of calcium stearate, and 0.05 kg of 264 antioxidant, continue to stir until the temperature of the material in the mixer rises to 120 ° C At 8 hours, add 8 kg of polylactic acid, discharge, and stir at low speed in a low-speed cooling mixer, cool, dehumidify, discharge, and package. Add the above powder to the meshing parallel co-rotating twin-screw extrusion sheet unit. The barrel temperature is 1 65 — 1 75 ° C, the die temperature is 1 45 ° C, the screw speed is 300 rpm, and the molar ratio of uniform injection is 0.75 kg. 1: 1 composite of methyl methacrylate and acetic anhydride, extruded sheet, calendered by a three-roll calender, cooled, shaped, and rolled to produce a sheet with a thickness of 0.2-2.5 mm, color Light yellow, delicate and shiny. Example 3 Take 40 kg of 100-mesh early rice starch, 2 kg of polyvinyl alcohol swelled with hot water, and 1.32 kg of paraffin wax, put them into a high-speed mixer that has been preheated to 7 (rc), turn on the stirring, and add 0.20 kg of stearic acid sequentially , 0.12 kg of zinc pyrrolidone stearate, 0.65 kg of calcium stearate, 0.05 μl of oleic acid, 0.50 kg of propylene glycol adipate polyester with a molecular weight of 1,000, and 0.02 kg of 264 antioxidant 'Continue to stir' The temperature of the material in the mixer rises to 1 丨 0 ° c and keep it for 5 minutes'. Discharge to the low-speed cooling mixer, stir at low speed, cool, dehumidify, discharge, and package. -15- (11) (11 ) 593514 H quarantine @ @ 粉料 added to the twin-screw extrusion sheet unit, barrel temperature 165 — Π 5 C 'die temperature H (rc, screw rotation speed 3,000 rpm, evenly injected a molar ratio of 1 · 20 kg is 1 : 1 compound of acrylamide and methacrylic anhydride 'extruded sheet material, calendered, cooled, shaped, rolled, and rolled to a thickness of 0.2 to 2.5 inin through a three-roll calender. , White, shiny Example 4 Weigh 48 kg of 100 mesh corn starch, 4 kg of polyvinyl acetate / polyacrylamide copolymer and 2 kg of stone fungus, put it into a high-speed mixer preheated to 70 ° C 'and continue stirring, and then add 0. 8 kg of dibenzyl sebacate, 0.25 kg of linolenic acid, 0.50 kg of stearic acid, 0. 52 kg of linoleamide, 0.10 kg of stearylamine, 0.12 kg of zinc stearate, and 0.16 kg of 1010 antioxidant 'continued to stir, and the temperature of the material in the mixer rose to 1 10. (: After maintaining 5 Discharge in minutes to the low-speed cooling mixer, cool, dehumidify, discharge, and pack. Add the above powder to the twin screw extruder sheet unit. The barrel temperature is 1 5 5 — 1 90 ° C, the die temperature is 150 ° C, screw rotation speed is 250 rpm. Compound of vinyl acetate and succinic acid with a molar ratio of 1: 1 to 0. 56 kg is uniformly added. Extruded sheet, calendered and cooled by a three-roll calender , Shape, and roll-up to make a sheet with a thickness of 0.2-2.5 mm, yellowish and shiny. Example 5 Take 48 kg of 100 mesh corn starch, 2 kg of konjac starch, 0.2 kg, polyethylene wax and 0.3 Add kg of stone concrete to a high-speed mixer that has been preheated to 70-80 ° C, turn it on and stir, and then add 0.7 1 kg of twelve within 16- (12) 593514 依次Amine, 0 · 12 kg of N, N-dibutylstearylamine, 0.27 kg of a composition of zinc stearate and stearic acid weighing 1 to 3 and 0.53 kg of apples, stirring continuously, etc. When it rises to 100-120 ° C, kg of polylactide is discharged into the low-speed cooling mixer, stirred at low speed, dehumidified, discharged, and packed. Add the above powder to the meshed parallel co-rotating twin-screw extruded sheet material. The barrel temperature is 1 65 — 1 85 ° C, the die temperature is 135 ° C, and the screw is rotated to rpm, and a 0.73 kg molar ratio of 1: 1 is injected. Extruded sheet of a compound of ethacrylic acid was calendered, cooled, and rolled by a three-roll calender to obtain a sheet with a thickness of 0.2-2.5 mm. The color was white. Example 6: 35 kg of 100-mesh corn starch A composition of 5 kg of early rice starch, paraffin wax, 1.0 kg of polypropylene wax, 0.42 kg of diisooctyl sebacate, kg of linoleic acid, and 1.12 kg of calcium magnesium stearate in a weight ratio of 3: 2, Add the high temperature machine which has been preheated to 70-80 ° C in turn. When the temperature of the material rises to 130 ° C, add 10 kg of poly (hydroxyester-valerate) copolymer, mix and discharge to low-speed cooling and mixing. Low speed stirring, cooling, dehumidifying, discharging, packaging. Add the above powder to the twin-screw extruding sheet unit. The barrel temperature is -1851, the die temperature is 1 3 5-1 4 5 ° C, the screw speed is 420 rpm, and the 0.64 kg methyl group with a molar ratio of 1: 1 is injected. The compound of propyl acrylate and enoic anhydride, extruded sheet, calendered Λ t stomach acid through a three-roll calender, followed by adding 3 mixing and cooling units, super 360 anhydride and benzene, setting gloss 0.5 kg '0.13 Mixed with stearin, the butyric acid machine has an internal degree of 160, uniform methyl propylene, cooling -17- (13) (13) 593514, setting, rolling, and producing a sheet with a thickness of 0.2-2.5 mm, with a slight color Yellow and shiny. Example 7: Take 40 kg of 100-mesh wheat flour, 2.0 kg of konjac starch, 0.5 kg of paraffin wax and 0.2 kg of polypropylene wax, add them into a high-speed mixer preheated to 70-80 ° C, continue stirring, and then Add 0.81 kg of a composition of methoxyethyl oleate and N, N-dimethyloleamide in a weight ratio of 1 ·· 1, and 0.62 kg of zinc stearate in a weight ratio of 1: 4 to For the composition of calcium stearate, when the temperature of the material rises to 110-120 ° C, add 2.5 kg of polyethylene glycol and discharge into a low-speed cooling mixer. Stir at low speed, cool, dehumidify, discharge, and package. The above materials are added to a twin-screw extruding sheet unit. The barrel temperature is i 30-155 ° C, the die temperature is 120-130 ° C, the screw speed is 1 70-1 90 rpm, and the molar ratio of 1.62 kg is uniformly 1: 1 compound of vinyl acetate and maleic anhydride, extruded sheet, calendered, cooled, and shaped by a three-roll calender to obtain a sheet with a thickness of 0.2-2.5mm, slightly yellow, Shiny. Example 8 Take 55 kg of 100-mesh corn starch and 0.3 kg of microcrystalline paraffin, put them into a heating high-speed mixer that has been preheated to 70 ° C, start up and stir, and add 15 kg of polyethylene and 0.26 kg of oleic acid in order. 〇.32 kg compound with a weight ratio of 4: 1: 1: calcium stearate / zinc stearate / butyl epoxy oleate and 0.06 kg -18- (14) 1 〇 1 0 Antioxidant, continue to stir. When the temperature of the material in the mixer rises to 100 ° C-120 ° C, discharge to the low-speed cooling mixer, and stir, cool, dehumidify, discharge, and package at low speed. Add the above powder to the twin screw extruder sheet unit. The barrel temperature is 160 ° C-200 ° C, the die temperature is 155t, and the screw speed is 250-300 rpm. The molar ratio of 0 · 4 0 kg is evenly 1: 1 is a complex of styrene and maleic anhydride. The sheet is extruded and calendered, cooled, shaped, and rolled by a three-roll calender to obtain a sheet with a thickness of 0.20-2.50 mm, which is slightly yellow in color and shiny. Example 9 Take 36 kg of sweet potato starch, 0.25 kg of microcrystalline paraffin wax and 0.70 kg of polypropylene tincture, put it into a heating high-speed mixer that has been preheated to 70 ° C, start up and stir, and add 0. 65 kg in weight ratio to 3 : 1 compound of oleylamine and butyl epoxy oleate, 2.85 kg weight ratio of 1: 3: 1 compound of ferrous oleate / calcium stearate / stearic acid, 10 kg of polypropylene And 0.12 kg of 264 antioxidant, continue to stir, when the temperature of the material in the mixer rises to il0 ° C -1 20 ° C, discharge to the low-speed cooling mixer, low-speed stirring, cooling, dehumidification, discharge, packaging . Add the above powder to the twin screw extruder sheet unit, the barrel temperature is 180 ° C-22 (TC, the die temperature is 150 ° C, the screw speed is 350 rpm. Evenly add 2.4 kg in a molar ratio of 1: 1 A composite of styrene and maleic anhydride. Extruded sheet, calendered, cooled, shaped, and rolled by a three-roll calender to produce a sheet with a thickness of 0.2-2.5 mm, white and shiny.- 19- (15) (15) 593514 The mechanical properties and degradation properties of the materials prepared in the above examples were determined as follows:

Example No. Tensile strength (20 ° C) (GB 1 040) MPa Degradability (grading) (GB 1 8006 · 1 — 1 999) 1 21 V 2 18 V 3 16 V 4 24 V 5 13 V 6 28 V 7 19 V 8 21 V 9 32 V The degradation performance in the above table was determined according to IS0846- 1 997: The fungus was inoculated on the surface of various samples, cultured under a certain temperature and humidity conditions, and observed after 28 days The growth of fungi on the surface of various samples is graded as follows to evaluate the degradation performance of the sample: -20- (16) Degradation performance is divided into fungal growth level 0 0 No fungus growth under the microscope __ 1 (I) No visible to the naked eye Growth, but clearly visible under the microscope 2 (II) visible growth with the naked eye, covering less than 25% of the sample surface 3 (III) visible growth with the naked eye, covering less than 50% of the sample surface 4 (IV 5) Obvious growth is visible to the naked eye, covering more than 50% of the sample surface 5 (V) is lush and covers the entire sample surface 593514 The present invention has multiple uses (1) The sheet of the present invention is subjected to a negative pressure thermoforming machine Continuous vacuum blistering into a variety of lunch boxes with flip lids Various shapes of plates, boxes, dishes, etc .; (2) The sheet of the present invention is continuously and positively thermoformed by a positive pressure thermoforming machine into cups, boxes, bowls, buckets (for instant noodles) of various specifications and shapes. (3) The leftovers, scraps, and defective products of the present invention can be recycled multiple times, and then processed into products without discoloration and performance. (4) The present invention can also be made into various packaging containers and shock-absorbing materials. The product of this invention has been inspected by the National Plastics Product Quality Supervision and Inspection Center and Railway-21-(17) (17) 593514 Ministry of Quality Supervision and Inspection Center Safety and Health Inspection Station, and its physical and chemical health indicators, use performance, and biodegradability are in line with the state The technical requirements for edible starch products in the standard GB 1 8006 1-1 999, but the cost is significantly lower than similar products at home and abroad. The starch-based biodegradable material of the present invention can be identified by the following convenient, quick, accurate and reliable method: when the product of the present invention is ignited, there is no dripping of molten matter, and it will turn into white or gray ash after complete combustion. For products made with polyolefin as the main raw material and filled with a small amount of starch and mineral powder or color masterbatch, the molten material drips when ignited, emits black smoke, odor, and forms a very hard black plastic block when the flame is extinguished . -twenty two-

Claims (1)

593514 (1) Pick up and apply for the amendment of the patent model I and replace this Annex II. No. 9 2 1 0 6 5 1 5 Patent Application Chinese Application Patent Scope Unlined Replacement April 26, 1993 Amendment 1. A kind of starch Based biodegradable material, which includes the following components: 65-95% by weight of plant starch, 1- 15% by weight of a reactive plasticizer, the reactive plasticizer is selected from the group consisting of aliphatic carboxylic acid, fat One or more of the low-molecular-weight polyesters, aliphatic amidoamines, aliphatic residual acid esters, and aliphatic residual acid metal salts, from 0.1 to 5% by weight, selected from comonomers having a molar ratio of 1 ·· 1 Reactive compatibilizer with a complex of acid anhydride or derivative thereof, wherein the comonomer is selected from the group consisting of acrylonitrile, vinyl acetate, acrylamide, isoprene, acrylic acid, alkyl methacrylate, and styrene One or more of them; the anhydride or derivative thereof is one or more selected from the group consisting of acetic anhydride, methacrylic anhydride, succinic anhydride, maleic anhydride, and maleimide, and 1-20% by weight of biodegradable Degradable polymer compounds, said biodegradable The polymer compound is selected from the group consisting of polycaprolactone, polyethylene glycol, polylactide, polylactic acid, polyhydroxybutyrate-valerate copolymer, polyethylene glycol, polyvinyl acetate-polyacrylamide copolymer And one or more of polyethylene and polypropylene modified by the reactive compatibilizer. 2. If the scope of patent application is the first! Item of the starch-based biodegradable material, wherein: the plant starch is selected from the group consisting of sweet potato starch, potato starch, cassava starch, konjac starch, corn starch, wheat flour, and early rice starch ~ (2) (2) 593514 species Or more. 3. The starch-based biodegradable material according to item 1 of the scope of patent application, wherein: the aliphatic carboxylic acid as the reactive plasticizer is selected from the group consisting of oleic acid, linoleic acid, stearic acid, and palmitic acid One, or more of adipic acid, lauric acid, myristic acid, linolenic acid, succinic acid, malic acid, worm wax acid, and flea wax acid. 4. The starch-based biodegradable material according to item 1 of the scope of the patent application, wherein the aliphatic ammonium as the reactive plasticizer is selected from urea, oleylamine, stearylamine, and linoleylamine One or more of amine, naphthene, caprolactam, dodecylamine, N, N-dibutylstearylamine, and N, N-dimethyloleylamine. 5. The starch-based biodegradable material according to item 1 of the patent application scope, wherein the metal salt of the aliphatic carboxylic acid as the reactive plasticizer is selected from the group consisting of oleic acid, ferrous oleate, hard One or more of magnesium stearate, ferrous stearate, golden stearate 'zinc stearate, manganese stearate and zinc pyrrolidone stearate. 6. The starch-based biodegradable material according to item 1 of the application, wherein the aliphatic carboxylic acid ester as the reactive plasticizer is selected from methoxyethyl oleate and diisooctyl sebacate One or more of esters, dibutoxyethyl adipate, diethyl sebacate, isooctyl sebacate nylon, butyl epoxy oleate and butyl ricinoleate. 7. The starch-based biodegradable material according to item 1 of the application, wherein the reactive plasticizer is an unterminated propylene glycol adipate polyester having a molecular weight of 300 to 1,200. (3) (3) 593514 8 · The starch-based biodegradable material according to item 1 of the patent application scope, wherein: the reactive compatibilizer composition is a 1: 1 composition of styrene and maleic anhydride . 9. The starch-based biodegradable material according to item 1 of the patent application scope, which additionally comprises 0.1 to 3% by weight of one or more physical plasticizers selected from paraffin wax, polyethylene wax, polypropylene tincture, and liquid paraffin. 10. The starch-based biodegradable material according to item 1 or 9 of the patent application scope, which further comprises a material selected from the group consisting of 2.6-disecond butyl-4-cresol, 1,1,3-tris (2-methyl- An antioxidant for 4-hydroxy-5-second butylphenyl) butane and tetrakis [3- (3,5-disecond butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester. 1 1. A method for preparing a starch-based biodegradable material as described in item 1 of the patent application scope, comprising the following steps: 1) adding plant starch and said reactive plasticizer to a high-speed mixer for mixing, 2) When the temperature rises to 80-20 (the biodegradable polymer compound is added when the temperature is TC, 3) the temperature is reduced to obtain the powder, 4) the above powder is added to the twin-screw extruder, and at 1 20- 230 1: Add the reactive compatibilizer, extrude the sheet, and then calender, cool, and shape. 1 2 · The starch-based bio-degradable material as described in item 1 of the scope of patent application, which is used to manufacture disposable food utensils, packaging containers and shock-absorbing materials.