CN112111017A - Degradable cassava acetate starch, resin thereof, preparation method and application of degradable cassava acetate starch and resin - Google Patents
Degradable cassava acetate starch, resin thereof, preparation method and application of degradable cassava acetate starch and resin Download PDFInfo
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Abstract
The embodiment of the invention discloses degradable cassava acetate starch, resin thereof, and preparation and application of the degradable cassava acetate starch and the resin, and relates to the fields of high polymer materials, thin film products, plastic-coated products, molded products, packaging materials, printing materials, electronic information industry film materials and the like. The degradable cassava acetate starch resin disclosed by the embodiment of the invention has good processing mechanical property, high breaking strength and tensile strength, strong water barrier property, excellent heat resistance and 70% of biodegradability, is environment-friendly, solves the problem of environmental pollution caused by plastic product wastes, saves the global forest resources to replace paper for printing and packaging, realizes the replacement of expensive PLA polylactic acid, has simple production process and low cost, and has greater significance for the research and application of new-technology environment-friendly degradable materials.
Description
Technical Field
The invention belongs to a high polymer material, and relates to the technical and application fields of biomedicine, medical equipment, sanitary dressing, printing material, electronic information industrial material, packaging material, blow molding film, injection molding product, calendering film product, casting stretching product, plastic coating film product, food packaging material, disposable tableware, disposable straw, disposable paper cup and other material fields, in particular to degradable cassava acetate starch, resin thereof, and preparation and application of the degradable cassava acetate starch and the resin.
Background
As is well known, the white pollution problem of plastic products seriously threatens and phagocytizes the ecological environment of the earth, and the main reason is that the components of the plastic products are organic hydrocarbons, such as high molecular plastic products and plastic films of PE polyethylene, PP polypropylene, PVC polyethylene, PS polystyrene and the like, and the final waste of the plastic products cannot be decomposed into small molecules or biodegraded in soil, rivers or oceans, so that irreparable threats and disasters are left.
In recent years, as many as dozens of PLA polylactic acid type degradable polymer materials are developed, produced and used in many ways. Although the problem of partial white pollution is relieved, the current price of PLA is 35-55 yuan/kg, the price is high, and the cost factor existing in the practical popularization and consumption mechanism cannot be borne at all, so that the comprehensive production, popularization and application of the PLA are hindered.
In view of the above, the invention provides a degradable cassava acetate starch resin, which has good processing mechanical properties, high breaking strength and longitudinal and transverse tensile strength, strong water barrier property, excellent heat resistance, and more than 70% of biodegradation property, has no toxic gas generated by directly burning wastes, is eco-friendly, effectively solves the problem of environmental pollution caused by the consumption wastes such as plastic products, film materials, packaging bags and the like, has simple production process and low cost, can be widely applied to replacing plastic products, film products and packaging bag products, saves the forest resources of the earth to replace paper printing and packaging purposes, not only solves the problem of environmental pollution caused by the wastes of the plastic products, but also realizes replacing expensive PLA polylactic acid, independently develops and produces a degradable cassava acetate starch resin film with low cost, has remarkable economic benefits, and is used for research development and application of new-technology environment-friendly degradable materials, also has greater significance.
Disclosure of Invention
The invention aims to solve the problem of severe white pollution caused by the incapability of degrading plastic products, and simultaneously aims at the defects of high cost of PLA polylactic acid and cost factors which prevent the comprehensive popularization and application of degradable materials.
The degradable cassava acetate starch is characterized by comprising the following raw materials in percentage by weight:
tapioca starch: 35% -37%;
acetic anhydride: 5% -9%;
sodium hydroxide: 3% -5%;
hydrogen peroxide: 0.5 to 1.50 percent;
deionized water: 48% -54.5%;
the above are all the total mass percentages.
Preferably, the raw materials comprise the following components in percentage by weight:
tapioca starch: 35% -37%;
acetic anhydride: 6.65% -7.35%;
sodium hydroxide: 3.80% -4.20%;
hydrogen peroxide: 0.95 to 1.05 percent;
deionized water: 51% -53%;
the above are all the total mass percentages.
Preferably, the raw materials also comprise the following components in percentage by weight:
sodium hypochlorite: 0 to 1.5 percent;
the above is the total mass percentage.
Preferably, the preparation method of the degradable cassava acetate starch comprises the following steps:
step (1): weighing deionized water and cassava starch according to a formula, sequentially injecting into a container 1, heating and stirring, controlling the temperature within a range of 44-46 ℃, and keeping the temperature and stirring;
step (2): weighing sodium hydroxide according to a formula, diluting with deionized water, dropwise adding the diluted sodium hydroxide into a container 1, performing alkalization treatment, continuously keeping the temperature within a range of 44-46 ℃, dropwise adding hydrogen peroxide into the container 1, controlling the temperature within a range of 44-46 ℃, and performing heat preservation and stirring;
and (3): after the step (2) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (4): after the step (3) is finished, additionally taking acetic anhydride, dropwise adding the acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (5): after the step (4), washing powder milk, performing cyclone separation, dehydrating and drying to prepare cassava acetate starch;
the ratio of acetic anhydride in the step (3) to acetic anhydride in the step (4) is 1: 1.
Preferably, the preparation method of the degradable cassava acetate starch comprises the following steps:
step (1): weighing deionized water and cassava starch according to a formula, sequentially injecting into a container 1, heating and stirring, controlling the temperature within a range of 44-46 ℃, and keeping the temperature and stirring;
step (2): weighing sodium hydroxide according to a formula, diluting with deionized water, dropwise adding into a container 1, and performing alkalization treatment;
and (3): after the step (2) is finished, dropwise adding hydrogen peroxide and/or sodium hypochlorite into the container 1 within the temperature range of 44-46 ℃, and continuing to keep the temperature and stir;
and (4): after the step (3) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (5): after the step (4) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (6): after the step (5), washing powder milk, performing cyclone separation, dehydrating and drying to prepare cassava acetate starch;
the ratio of acetic anhydride in the step (4) to acetic anhydride in the step (5) is 1: 1.
The degradable cassava acetate starch resin is characterized by comprising the following raw material components: cassava acetate starch, a plasticizer, a stabilizer, a degrading agent, a cross-linking agent and a lubricating agent;
the plasticizer is one or more of Epoxidized Soybean Oil (ESO), diethyl phthalate (DEP), dimethyl phthalate (DMP), Ethylene Glycol (EG), polyethylene glycol (PEG) and acetyl tributyl citrate (ATBC);
the stabilizer is dimethyl tin mercaptide;
the degradation agent is ethylene glycol;
the cross-linking agent is dicumyl peroxide;
the lubricant is oleamide;
the cassava acetate starch is the cassava acetate starch.
Preferably, the plasticizer is epoxidized soybean oil.
Preferably, the content of each raw material component is as follows:
cassava acetate starch: 67.2-70.7%;
plasticizer epoxidized soybean oil: 25.3-28.8%;
stabilizer dimethyltin mercaptide: 0.3 to 0.5 percent;
the degradation agent is glycol: 1.05 to 1.5 percent
Crosslinking agent dicumyl peroxide: 0.56% -0.8%;
lubricant oleamide: 0.84% -1.2%;
the above are all the total mass percentages.
Preferably, the degradable cassava acetate starch resin further comprises polyvinyl alcohol as a raw material component;
the polyvinyl alcohol is one or more of PVA-1788 polyvinyl alcohol, PVA-2088 polyvinyl alcohol and PVA-2488 polyvinyl alcohol, or PVA-1799 polyvinyl alcohol, PVA-2099 polyvinyl alcohol and PVA-2499 polyvinyl alcohol;
the contents of the raw material components are as follows:
cassava acetate starch: 53.5% -68%;
polyvinyl alcohol: 0 to 14.5 percent;
plasticizer: 23% -26%;
a stabilizer: 0.2 to 0.5 percent;
a degradation agent: 4.5-6.5%;
a crosslinking agent: 0.5 to 0.8 percent;
lubricant: 0.8 to 1.2 percent;
the above are all the total mass percentages.
Preferably, the degradable cassava acetate starch resin,
the method comprises the following steps of (1) obtaining resins with different processing mechanical properties by adjusting the proportion of cassava acetate starch to polyvinyl alcohol in an interactive manner by equivalent amounts of other raw material components, and obtaining the progressive increase of the tensile strength of the resins when the dosage of the polyvinyl alcohol is increased; when the dosage of the cassava acetate starch is increased, the tensile strength of the obtained resin is decreased gradually.
Preferably, the degradable cassava acetate starch resin,
the plasticizer comprises acetyl tributyl citrate (ATBC) and polyethylene glycol (PEG), the proportion range of the acetyl tributyl citrate and the polyethylene glycol is 0.4-1.7, other raw material components are equal, the proportion of the acetyl tributyl citrate (ATBC) and the polyethylene glycol (PEG) are interactively regulated, and different resins with different processing mechanical properties are obtained: when the dosage of the polyethylene glycol is increased, the tensile strength is decreased progressively, and the longitudinal and transverse elongations are increased progressively; when the dosage of the acetyl tributyl citrate is increased, the tensile strength is increased gradually, and the longitudinal and transverse elongations are decreased gradually.
Preferably, the preparation method of the degradable cassava acetate starch resin comprises the following steps:
(1) vacuum drying of raw materials: dehydrating and drying the cassava acetate starch in vacuum to a completely anhydrous state;
(2) plasticizing and melting: weighing dried cassava acetate starch and a plasticizer according to a formula, and sequentially putting the cassava acetate starch and the plasticizer into a double-screw mixing mill reactor to be heated, melted and mixed to form a melt A with fluidity;
(3) melting and mixing of an auxiliary agent: weighing a stabilizer, a degrading agent and a cross-linking agent according to a formula, and sequentially adding the stabilizer, the degrading agent and the cross-linking agent into the melt A for melt mixing to form a melt B with fluidity;
(4) melting and mixing of a lubricant: weighing the lubricant according to the formula, and adding the lubricant into the melt B for homogenizing, melting and mixing to obtain a melt C;
(5) and melting and extruding the melt C, and synchronously freezing, sublimating, dehydrating, drying and granulating in the same direction to obtain the degradable cassava acetate starch resin.
Preferably, the preparation method of the degradable cassava acetate starch resin comprises the following steps:
(1) vacuum drying of raw materials: putting the cassava acetate starch into a vacuum oven for dehydration and drying until the cassava acetate starch is completely anhydrous;
(2) plasticizing and melting: weighing dehydrated and dried cassava acetate starch, a plasticizer and polyvinyl alcohol according to a formula, and sequentially putting the cassava acetate starch, the plasticizer and the polyvinyl alcohol into a double-screw mixing roll reactor to be heated, melted and mixed to form mixed resin with fluidity, so as to obtain a molten mass A;
(3) melting and mixing of an auxiliary agent: weighing a stabilizer, a degrading agent and a cross-linking agent according to a formula, and sequentially adding the stabilizer, the degrading agent and the cross-linking agent into the melt A for melt mixing to form a melt B with fluidity;
(4) melting and mixing of a lubricant: weighing the lubricant according to the formula, and adding the lubricant into the melt B for homogenizing, melting and mixing to obtain a melt C;
(5) and melting and extruding the melt C, synchronously freezing in the same direction, sublimating, dehydrating, drying and granulating to obtain the degradable cassava acetate starch resin.
Preferably, the application of the degradable cassava acetate starch resin in the degradable cassava acetate starch resin film comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): and putting the dehydrated and dried degradable cassava acetate starch resin into a charging barrel of a blow molding machine, and carrying out co-rotating double-screw melting, extrusion, film blowing and traction stretching to obtain a plastic-substituted blown film, namely the degradable cassava acetate starch resin blown film.
Preferably, the application of the degradable cassava acetate starch resin in preparing the alternative casting stretching plastic film comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): melt extrusion casting stretching: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a casting machine for melt extrusion, and performing casting stretching to obtain a 15-100 mu m thick cast stretch film.
Preferably, the application of the degradable cassava acetate starch resin in preparing a plastic-coated product for replacing plastics comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): coating plastic and spraying film: and extracting the anhydrous degradable cassava acetate starch resin, putting the extracted anhydrous degradable cassava acetate starch resin into a charging barrel of a laminating machine, and carrying out co-rotating double-screw homogeneous melting extrusion coating on the surface of the paper medium to obtain the degradable cassava acetate starch resin plastic-coated laminating product.
Preferably, the application of the degradable cassava acetate starch resin in preparing a degradable injection molding product for replacing plastic comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): injection molding: and extracting the anhydrous degradable cassava acetate starch resin, putting the extracted anhydrous degradable cassava acetate starch resin into a charging barrel of an injection molding machine, carrying out homodromous double-screw homogeneous melting extrusion and compression molding, and preparing the degradable cassava acetate starch resin injection molded product.
Preferably, in the application of the degradable cassava acetate starch resin in preparing the degradable cassava acetate starch film, the method comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): melt extrusion casting stretching: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a casting machine for melt extrusion, casting and stretching, and preparing the degradable cassava acetate starch resin film material with the thickness of 200-500 mu m.
Preferably, the application of the degradable cassava acetate starch resin in preparing a substitute paper printing material comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): and (3) melting and quantitative blade coating of a calender: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a calender for melting and quantitative blade coating, and preparing the degradable cassava acetate starch resin printing material with the thickness of 125-270 mu m.
By adopting the technical scheme, the embodiment of the invention has the following beneficial effects:
1. the degradable cassava acetate starch resin prepared by the embodiment of the invention has good processing mechanical properties, the longitudinal tensile strength is more than or equal to 36MPa, the transverse tensile strength is more than or equal to 32MPa, the elongation at break is less than or equal to 175%, the water barrier property is more than 99.6%, the heat resistance is more than 60 ℃, the biodegradability is more than 70%, and the biodegradable property meets the biodegradability detection standard GB/T19277.
2. In the embodiment of the invention, the degradable cassava acetate starch resin is prepared by using powder milk of original ecological cassava starch as a core raw material and performing alkalization, esterification, dehydration, drying and plasticizing granulation, and the degradable cassava acetate starch resin film is prepared by using the degradable cassava acetate starch resin, and can replace plastic-coated and film-coated degradable products, plastic-injection molded degradable injection-molded products and plastic tape-cast and stretched film material degradable film products. The components of the formula belong to polysaccharide starch materials, the biodegradability is more than 70%, the waste is directly burned without generating toxic gas, the environment-friendly plastic product is environment-friendly, the problem of environmental pollution caused by consumable waste such as plastic products, film materials, packaging bags and the like is effectively solved, the special biodegradable plastic product accords with the industry which is important to encourage development in China, is a key prop product for replacing plastic products, solves the problem of white pollution threatening the ecological environment, accords with the industry development policy guidance and industry development planning related to various provinces and autonomous regions, and especially has greater significance for research development and application of new-technology environment-friendly degradable materials.
3. The degradable cassava acetate starch resin film or other related film materials prepared by the embodiment of the invention can replace plastic products and expensive PLA polylactic acid, has low production cost and simple method, effectively solves the problem of white pollution of plastics, overcomes the defect of expensive PLA polylactic acid, hinders the popularization, development and application of degradable materials, is beneficial to processing, producing and using high polymer materials and downstream terminal customers, has more obvious economic benefit, and has greater significance for environmental protection and safe production technical supervision.
Detailed Description
The degradable cassava acetate starch is characterized by comprising the following raw materials in percentage by weight:
tapioca starch: 35% -37%;
acetic anhydride: 5% -9%;
sodium hydroxide: 3% -5%;
hydrogen peroxide: 0.5 to 1.50 percent;
deionized water: 48% -54.5%;
the above are all the total mass percentages.
Preferably, the raw materials comprise the following components in percentage by weight:
tapioca starch: 35% -37%;
acetic anhydride: 6.65% -7.35%;
sodium hydroxide: 3.80% -4.20%;
hydrogen peroxide: 0.95 to 1.05 percent;
deionized water: 51% -53%;
the above are all the total mass percentages.
Preferably, the raw materials also comprise the following components in percentage by weight:
sodium hypochlorite: 0 to 1.5 percent;
the above is the total mass percentage.
Preferably, the method for degrading cassava acetate starch comprises the following steps:
step (1): weighing deionized water and cassava starch according to a formula, sequentially injecting into a container 1, heating and stirring, controlling the temperature within a range of 44-46 ℃, and keeping the temperature and stirring;
step (2): weighing sodium hydroxide according to a formula, diluting with deionized water, dropwise adding the diluted sodium hydroxide into a container 1, performing alkalization treatment, continuously keeping the temperature within a range of 44-46 ℃, dropwise adding hydrogen peroxide into the container 1, controlling the temperature within a range of 44-46 ℃, and performing heat preservation and stirring;
and (3): after the step (2) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (4): after the step (3) is finished, additionally taking acetic anhydride, dropwise adding the acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (5): after the step (4), washing powder milk, performing cyclone separation, dehydrating and drying to prepare cassava acetate starch;
the ratio of acetic anhydride in the step (3) to acetic anhydride in the step (4) is 1: 1.
Preferably, the preparation method of the degradable cassava acetate starch comprises the following steps:
step (1): weighing deionized water and cassava starch according to a formula, sequentially injecting into a container 1, heating and stirring, controlling the temperature within a range of 44-46 ℃, and keeping the temperature and stirring;
step (2): weighing sodium hydroxide according to a formula, diluting with deionized water, dropwise adding into a container 1, and performing alkalization treatment;
and (3): after the step (2) is finished, dropwise adding hydrogen peroxide and/or sodium hypochlorite into the container 1 within the temperature range of 44-46 ℃, and continuing to keep the temperature and stir;
and (4): after the step (3) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (5): after the step (4) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (6): after the step (5), washing powder milk, performing cyclone separation, dehydrating and drying to prepare cassava acetate starch;
the ratio of acetic anhydride in the step (4) to acetic anhydride in the step (5) is 1: 1.
The degradable cassava acetate starch resin is characterized by comprising the following raw material components: cassava acetate starch, a plasticizer, a stabilizer, a degrading agent, a cross-linking agent and a lubricating agent;
the plasticizer is one or more of Epoxidized Soybean Oil (ESO), diethyl phthalate (DEP), dimethyl phthalate (DMP), Ethylene Glycol (EG), polyethylene glycol (PEG) and acetyl tributyl citrate (ATBC);
the stabilizer is dimethyl tin mercaptide;
the degradation agent is ethylene glycol;
the cross-linking agent is dicumyl peroxide;
the lubricant is oleamide;
the cassava acetate starch is the cassava acetate starch described above.
Preferably, the plasticizer is epoxidized soybean oil.
Preferably, the content of each raw material component is as follows:
cassava acetate starch: 67.2-70.7%;
plasticizer epoxidized soybean oil: 25.3-28.8%;
stabilizer dimethyltin mercaptide: 0.3 to 0.5 percent;
the degradation agent is glycol: 1.05 to 1.5 percent
Crosslinking agent dicumyl peroxide: 0.56% -0.8%;
lubricant oleamide: 0.84% -1.2%;
the above are all the total mass percentages.
Preferably, the degradable cassava acetate starch resin further comprises polyvinyl alcohol as a raw material component;
the polyvinyl alcohol is one or more of PVA-1788 polyvinyl alcohol, PVA-2088 polyvinyl alcohol and PVA-2488 polyvinyl alcohol, or PVA-1799 polyvinyl alcohol, PVA-2099 polyvinyl alcohol and PVA-2499 polyvinyl alcohol;
the contents of the raw material components are as follows:
cassava acetate starch: 53.5% -68%;
polyvinyl alcohol: 0 to 14.5 percent;
plasticizer: 23% -26%;
a stabilizer: 0.2 to 0.5 percent;
a degradation agent: 4.5-6.5%;
a crosslinking agent: 0.5 to 0.8 percent;
lubricant: 0.8 to 1.2 percent;
the above are all the total mass percentages.
Preferably, the degradable cassava acetate starch resin,
the method comprises the following steps of (1) obtaining resins with different processing mechanical properties by adjusting the proportion of cassava acetate starch to polyvinyl alcohol in an interactive manner by equivalent amounts of other raw material components, and obtaining the progressive increase of the tensile strength of the resins when the dosage of the polyvinyl alcohol is increased; when the dosage of the cassava acetate starch is increased, the tensile strength of the obtained resin is decreased gradually.
Preferably, the degradable cassava acetate starch resin,
the plasticizer comprises acetyl tributyl citrate (ATBC) and polyethylene glycol (PEG), the proportion range of the acetyl tributyl citrate and the polyethylene glycol is 0.4-1.7, other raw material components are equal, the proportion of the acetyl tributyl citrate (ATBC) and the polyethylene glycol (PEG) are interactively regulated, and different resins with different processing mechanical properties are obtained: when the dosage of the polyethylene glycol is increased, the tensile strength is decreased progressively, and the longitudinal and transverse elongations are increased progressively; when the dosage of the acetyl tributyl citrate is increased, the tensile strength is increased gradually, and the longitudinal and transverse elongations are decreased gradually.
Preferably, the preparation method of the degradable cassava acetate starch resin comprises the following steps:
(1) vacuum drying of raw materials: dehydrating and drying the cassava acetate starch in vacuum to a completely anhydrous state;
(2) plasticizing and melting: weighing dried cassava acetate starch and a plasticizer according to a formula, and sequentially putting the cassava acetate starch and the plasticizer into a double-screw mixing mill reactor to be heated, melted and mixed to form a melt A with fluidity;
(3) melting and mixing of an auxiliary agent: weighing a stabilizer, a degrading agent and a cross-linking agent according to a formula, and sequentially adding the stabilizer, the degrading agent and the cross-linking agent into the melt A for melt mixing to form a melt B with fluidity;
(4) melting and mixing of a lubricant: weighing the lubricant according to the formula, and adding the lubricant into the melt B for homogenizing, melting and mixing to obtain a melt C;
(5) and melting and extruding the melt C, and synchronously freezing, sublimating, dehydrating, drying and granulating in the same direction to obtain the degradable cassava acetate starch resin.
Preferably, the preparation method of the degradable cassava acetate starch resin comprises the following steps:
(1) vacuum drying of raw materials: putting the cassava acetate starch into a vacuum oven for dehydration and drying until the cassava acetate starch is completely anhydrous;
(2) plasticizing and melting: weighing dehydrated and dried cassava acetate starch, a plasticizer and polyvinyl alcohol according to a formula, and sequentially putting the cassava acetate starch, the plasticizer and the polyvinyl alcohol into a double-screw mixing roll reactor to be heated, melted and mixed to form mixed resin with fluidity, so as to obtain a molten mass A;
(3) melting and mixing of an auxiliary agent: weighing a stabilizer, a degrading agent and a cross-linking agent according to a formula, and sequentially adding the stabilizer, the degrading agent and the cross-linking agent into the melt A for melt mixing to form a melt B with fluidity;
(4) melting and mixing of a lubricant: weighing the lubricant according to the formula, and adding the lubricant into the melt B for homogenizing, melting and mixing to obtain a melt C;
(5) and melting and extruding the melt C, synchronously freezing in the same direction, sublimating, dehydrating, drying and granulating to obtain the degradable cassava acetate starch resin.
Preferably, the application of the degradable cassava acetate starch resin in the degradable cassava acetate starch resin film comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): and putting the dehydrated and dried degradable cassava acetate starch resin into a charging barrel of a blow molding machine, and carrying out co-rotating double-screw melting, extrusion, film blowing and traction stretching to obtain a plastic-substituted blown film, namely the degradable cassava acetate starch resin blown film.
Preferably, the application of the degradable cassava acetate starch resin in preparing the alternative casting stretching plastic film comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): melt extrusion casting stretching: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a casting machine for melt extrusion, and performing casting stretching to obtain a 15-100 mu m thick cast stretch film.
Preferably, the application of the degradable cassava acetate starch resin in preparing a plastic-coated product for replacing plastics comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): coating plastic and spraying film: and extracting the anhydrous degradable cassava acetate starch resin, putting the extracted anhydrous degradable cassava acetate starch resin into a charging barrel of a laminating machine, and carrying out co-rotating double-screw homogeneous melting extrusion coating on the surface of the paper medium to obtain the degradable cassava acetate starch resin plastic-coated laminating product.
Preferably, the application of the degradable cassava acetate starch resin in preparing a degradable injection molding product for replacing plastic comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): injection molding: and extracting the anhydrous degradable cassava acetate starch resin, putting the extracted anhydrous degradable cassava acetate starch resin into a charging barrel of an injection molding machine, carrying out homodromous double-screw homogeneous melting extrusion and compression molding, and preparing the degradable cassava acetate starch resin injection molded product.
Preferably, the application of the degradable cassava acetate starch resin in preparing the degradable cassava acetate starch film material comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): melt extrusion casting stretching: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a casting machine for melt extrusion, casting and stretching, and preparing the degradable cassava acetate starch resin film material with the thickness of 200-500 mu m.
Preferably, the application of the degradable cassava acetate starch resin in preparing a substitute paper printing material comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): and (3) melting and quantitative blade coating of a calender: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a calender for melting and quantitative blade coating, and preparing the degradable cassava acetate starch resin printing material with the thickness of 125-270 mu m.
The present invention will be explained by the following examples and comparative examples.
Example 1:
the formula of the cassava acetate starch comprises:
tapioca starch: 36 percent
Acetic anhydride: 7 percent of
Sodium hydroxide: 4 percent of
Hydrogen peroxide: 1 percent of
Deionized water: 52%:
the above are all the total mass percentages.
The formula of the degradable cassava acetate starch resin comprises the following components:
cassava acetate starch: 67.2 percent;
plasticizer Epoxidized Soybean Oil (ESO): 28.8 percent;
stabilizer dimethyltin mercaptide (abbreviation 181): 0.5 percent;
degradant Ethylene Glycol (EG): 1.5 percent
Crosslinking agent dicumyl peroxide (DCP): 0.8 percent;
lubricant Oleamide (Oleamide): 1.2 percent;
the above are all the total mass percentages.
Example 2: the formula of the cassava acetate starch is the same as that of the example 1, the degradable cassava acetate starch resin formula takes the example 1 as a reference, the increment of the cassava acetate starch is 1.5 percent, the decrement of the plasticizer, namely the epoxy soybean oil is 1.5 percent, and the rest are unchanged;
cassava acetate starch: 68.7 percent;
plasticizer Epoxidized Soybean Oil (ESO): 27.3 percent;
stabilizer dimethyltin mercaptide (abbreviation 181): 0.5 percent;
degradant Ethylene Glycol (EG): 1.5 percent
Crosslinking agent dicumyl peroxide (DCP): 0.8 percent;
lubricant Oleamide (Oleamide): 1.2 percent;
the above are all the total mass percentages.
Example 3: the formula of the cassava acetate starch is the same as that of the example 1, the formula of the degradable cassava acetate starch resin is based on the example 1, the increment of the cassava acetate starch is 2%, the decrement of the plasticizer, namely the epoxy soybean oil is 2%, and the rest are unchanged;
cassava acetate starch: 69.2 percent;
plasticizer Epoxidized Soybean Oil (ESO): 26.8 percent;
stabilizer dimethyltin mercaptide (abbreviation 181): 0.5 percent;
degradant Ethylene Glycol (EG): 1.5 percent
Crosslinking agent dicumyl peroxide (DCP): 0.8 percent;
lubricant Oleamide (Oleamide): 1.2 percent;
the above are all the total mass percentages.
Example 4: the formula of the cassava acetate starch is the same as that of the example 1, the degradable cassava acetate starch resin formula takes the example 1 as a reference, the increment of the cassava acetate starch is 2.5 percent, the decrement of the plasticizer, namely the epoxy soybean oil is 2.5 percent, and the rest are unchanged;
cassava acetate starch: 69.7 percent;
plasticizer Epoxidized Soybean Oil (ESO): 26.3 percent;
stabilizer dimethyltin mercaptide (abbreviation 181): 0.5 percent;
degradant Ethylene Glycol (EG): 1.5 percent
Crosslinking agent dicumyl peroxide (DCP): 0.8 percent;
lubricant Oleamide (Oleamide): 1.2 percent;
the above are all the total mass percentages.
Example 5: the formula of the cassava acetate starch is the same as that in the example 1, the degradable cassava acetate starch resin formula takes the example 1 as a reference, the increment of the cassava acetate starch is 3 percent, the decrement of the plasticizer, namely epoxidized soybean oil is 3 percent, and the rest are unchanged;
cassava acetate starch: 70.2 percent;
plasticizer Epoxidized Soybean Oil (ESO): 25.8 percent;
stabilizer dimethyltin mercaptide (abbreviation 181): 0.5 percent;
degradant Ethylene Glycol (EG): 1.5 percent
Crosslinking agent dicumyl peroxide (DCP): 0.8 percent;
lubricant Oleamide (Oleamide): 1.2 percent;
the above are all the total mass percentages.
Comparative example 1: the formula of the cassava acetate starch is the same as that of the example 1, and the formula of the degradable cassava acetate starch resin is as follows, because the dosage of the plasticizer is increased, the cohesive strength is influenced, and the strength resistance and the elongation at break are obviously reduced.
Cassava acetate starch: 65.7 percent;
plasticizer Epoxidized Soybean Oil (ESO): 30.3 percent;
stabilizer dimethyltin mercaptide (abbreviation 181): 0.5 percent;
degradant Ethylene Glycol (EG): 1.5 percent
Crosslinking agent dicumyl peroxide (DCP): 0.8 percent;
lubricant Oleamide (Oleamide): 1.2 percent;
the above are all the total mass percentages.
Example 6:
the formula of the degradable cassava acetate starch comprises the following components in percentage by mass:
tapioca starch: 36.0 percent
Acetic anhydride: 7.0 percent
Sodium hydroxide: 4.0 percent
Hydrogen peroxide: 1.0 percent
Deionized water: 52.0%:
the above are all the total mass percentages.
The formula of the degradable cassava acetate starch resin comprises the following components in percentage by mass:
cassava acetate starch: 59.2 percent;
polyvinyl alcohol PVA-1788: 8.8 percent;
plasticizer a acetyl tributyl citrate: 13.0 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.5 percent;
the degradation agent is glycol: 4.5 percent;
crosslinking agent dicumyl peroxide: 0.8 percent;
lubricant oleamide: 1.2 percent;
the above are all the total mass percentages.
Example 7
The formula of the degradable cassava acetate starch comprises the following components in percentage by mass:
tapioca starch: 35.0 percent
Acetic anhydride: 9.0 percent
Sodium hydroxide: 3.0 percent
Hydrogen peroxide: 0.5 percent
Sodium hypochlorite: 1.5 percent
Deionized water: 51%:
the above are all the total mass percentages.
The formula of the degradable cassava acetate starch resin comprises the following components in percentage by mass:
cassava acetate starch: 59.2 percent;
polyvinyl alcohol PVA-1788: 8.8 percent;
plasticizer a acetyl tributyl citrate: 13.0 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.0 percent;
the degradation agent is glycol: 4.50 percent;
crosslinking agent dicumyl peroxide: 0.8 percent;
lubricant oleamide: 1.20 percent;
the above are all the total mass percentages.
Example 8
The formula of the degradable cassava acetate starch comprises the following components in percentage by mass:
tapioca starch: 37.0 percent
Acetic anhydride: 5.0 percent
Sodium hydroxide: 5.0 percent
Hydrogen peroxide: 1.5 percent
Sodium hypochlorite: 0.5 percent
Deionized water: 51.0%:
the above are all the total mass percentages.
The formula of the degradable cassava acetate starch resin comprises the following components in percentage by mass:
cassava acetate starch: 59.2;
polyvinyl alcohol PVA-1788: 8.8 percent;
plasticizer a acetyl tributyl citrate: 13.0 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.5 percent;
the degradation agent is glycol: 4.5 percent;
crosslinking agent dicumyl peroxide: 0.8 percent;
lubricant oleamide: 1.2 percent;
the above are all the total mass percentages.
Example 9: the formula of the cassava acetate starch is the same as that in the example 6, the formula of the degradable cassava acetate starch resin is based on the example 6, the increment of the cassava acetate starch is 1.5 percent, the decrement of the plasticizer A of the acetyl tributyl citrate is 1.5 percent, and the rest components are unchanged;
cassava acetate starch: 60.7 percent;
polyvinyl alcohol PVA-1788: 8.8 percent;
plasticizer a acetyl tributyl citrate: 11.5 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.5 percent;
the degradation agent is glycol: 4.5 percent;
crosslinking agent dicumyl peroxide: 0.8 percent;
lubricant oleamide: 1.2 percent;
the above are all the total mass percentages.
Example 10: the formula of the cassava acetate starch is the same as that in the example 6, the formula of the degradable cassava acetate starch resin is based on the example 6, the increment of the cassava acetate starch is 2.0 percent, the decrement of the plasticizer A acetyl tributyl citrate is 2.0 percent, and the rest is unchanged;
cassava acetate starch: 61.2 percent;
polyvinyl alcohol PVA-1788: 8.8 percent;
plasticizer a acetyl tributyl citrate: 11.0 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.5 percent;
the degradation agent is glycol: 4.5 percent;
crosslinking agent dicumyl peroxide: 0.8 percent;
lubricant oleamide: 1.2 percent;
the above are all the total mass percentages.
Example 11: the formulation of the tapioca acetate starch was the same as that of example 6, and the formulation of the degradable tapioca acetate starch resin was as follows:
cassava acetate starch: 53.5 percent;
polyvinyl alcohol PVA-1788: 14.5 percent;
plasticizer a acetyl tributyl citrate: 12.0 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.2 percent;
the degradation agent is glycol: 6.5 percent;
crosslinking agent dicumyl peroxide: 0.5 percent;
lubricant oleamide: 0.8 percent;
the above are all the total mass percentages.
Example 12: the formulation of the tapioca acetate starch was the same as that of example 6, and the formulation of the degradable tapioca acetate starch resin was as follows:
cassava acetate starch: 68 percent;
polyvinyl alcohol PVA-1788: 0;
plasticizer a acetyl tributyl citrate: 12.5 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.3 percent;
the degradation agent is glycol: 5.5 percent;
crosslinking agent dicumyl peroxide: 0.7 percent;
lubricant oleamide: 1.0 percent;
the above are all the total mass percentages.
Example 13
The polyvinyl alcohol was PVA-2088 polyvinyl alcohol, and the rest was the same as in example 6.
Example 14
The polyvinyl alcohol was PVA-2488 polyvinyl alcohol, and the other examples were the same as in example 6.
Example 15
The polyvinyl alcohol was PVA-1799 polyvinyl alcohol, and the rest was the same as in example 6.
Example 16
The polyvinyl alcohol was PVA-2099 polyvinyl alcohol, and the rest was the same as in example 6.
Example 17
The polyvinyl alcohol was PVA-2499 polyvinyl alcohol, and the other examples were the same as in example 6.
Example 18
The polyvinyl alcohols were PVA-2099 polyvinyl alcohol and PVA-2499 polyvinyl alcohol at a ratio of 1:1, and the rest was the same as in example 6.
Example 19
The polyvinyl alcohol was PVA-2088 polyvinyl alcohol and PVA-2499 polyvinyl alcohol at a ratio of 3:1, and the rest was the same as in example 6.
Example 20
The plasticizer A is diethyl phthalate (DEP) with the content of 11.0 percent; the plasticizer B is dimethyl phthalate (DMP) with the content of 14.0 percent; the rest is the same as in example 6.
Example 21
The plasticizer A is diethyl phthalate (DEP) with the content of 13.0 percent; plasticizer B is Epoxidized Soybean Oil (ESO), and the content is 12.0%; the rest is the same as in example 6.
Example 22
The plasticizer A is Epoxidized Soybean Oil (ESO), and the content is 13.0 percent; the plasticizer B is Ethylene Glycol (EG), and the content is 12.0%; the rest is the same as in example 6.
Example 23
The plasticizer A and the plasticizer B are both Epoxidized Soybean Oil (ESO), and the content of the Epoxidized Soybean Oil (ESO) is 25.0%; the rest is the same as in example 6.
Example 24
The plasticizer A is diethyl phthalate (DEP) with the content of 8.0 percent; the plasticizer B is Ethylene Glycol (EG), and the content is 8.0%; the plasticizer C is polyethylene glycol (PEG), and the content is 7.0%; the rest is the same as in example 6.
Example 25
The plasticizer A is dimethyl phthalate (DMP) with the content of 5.0 percent; the plasticizer B is Ethylene Glycol (EG), and the content is 9.0%; plasticizer C is acetyl tributyl citrate (ATBC), and the content is 11.0%; the rest is the same as in example 6.
Comparative example 2: the formula of the cassava acetate starch is the same as that of the example 1, and the formula of the degradable cassava acetate starch resin is as follows, because the dosage of the plasticizer is increased, the cohesive strength is influenced, and the strength resistance and the elongation at break are obviously reduced.
Cassava acetate starch: 57.7 percent;
polyvinyl alcohol PVA-1788: 8.8 percent;
plasticizer a acetyl tributyl citrate: 14.5 percent;
plasticizer B polyethylene glycol: 12.0 percent;
stabilizer dimethyltin mercaptide: 0.5 percent;
the degradation agent is glycol: 4.5 percent;
crosslinking agent dicumyl peroxide: 0.8 percent;
lubricant oleamide: 1.2 percent;
the above are all the total mass percentages.
Quality and performance test methods and results for examples 1-25 and comparative examples 1-2:
and (3) performance detection: taking the degradable cassava acetate starch resin, and carrying out film blowing and stretching by a blow molding machine to prepare a degradable cassava acetate starch resin film with the thickness of 18 mu m, wherein the detection standard is as follows:
GT/B1040.3-2006 film tensile strength detection standard;
GB/T19277 biodegradability test standard;
GB/T4456 and 2008 for packaging use the polyethylene blow molding film national standard;
the definition of GB/T20197-2006 degradation plastic;
the detection contents are as follows:
examples the formulations performance test results are given in the following table:
the performance test results of the degradable cassava acetate starch resin films prepared in the above embodiments 1 to 5 can be known as follows:
the degradable cassava acetate starch resin film prepared by the embodiment of the invention has good structural mechanical property, the longitudinal tensile strength is more than 33MPa, the transverse tensile strength is more than 30MPa, the elongation at break is less than 180%, the water barrier property is more than 99.6%, the heat resistance is more than 60 ℃, the biodegradability is more than 70%, and the biodegradable film accords with the biodegradability detection standard GB/T19277.
In the component of the comparative example 1, the cohesive strength is affected due to the increase of the dosage of the plasticizer, so that the performances of the strength resistance and the elongation at break are obviously reduced.
The performance test results of the degradable cassava acetate starch resin films prepared in the above embodiments 6 to 25 can be seen as follows:
the degradable cassava acetate starch resin film prepared by the embodiment of the invention has good structural mechanical properties, the longitudinal tensile strength is more than or equal to 36MPa, the transverse tensile strength is more than or equal to 32MPa, the elongation at break is less than or equal to 175%, the water barrier property is more than 99.6%, the heat resistance is more than 60 ℃, the biodegradability is more than 70%, and the biodegradable film meets the biodegradability detection standard GB/T19277.
In the component of the comparative example 2, the cohesive strength is affected due to the increase of the dosage of the plasticizer, so that the performances of the strength resistance and the elongation at break are obviously reduced.
The embodiment of the invention is characterized in that the cassava acetate starch and plasticizer acetyl tributyl citrate component have intermodulation variation values to obtain degradable cassava acetate starch resin films with different mechanical properties, in the embodiment of the equivalent other raw material components, when the dosage of the cassava acetate starch is increased, the longitudinal tensile strength is more than or equal to 33MPa, the transverse tensile strength is more than 30MPa, and the elongation at break is less than or equal to 175%; in the comparison example, when the dosage of the plasticizer acetyl tributyl citrate component is increased, the longitudinal tensile strength is less than 33MPa, the transverse tensile strength is less than 30MPa, and the breaking elongation is more than 180 percent.
In the embodiment, due to the characteristic that the ratio of amylopectin to amylose in the tapioca starch is as high as 80:20, the amount of the tapioca acetate starch component is increased gradually to obtain the degradable tapioca acetate starch resin film which has different tensile strength, elongation at break, temperature resistance and leakage resistance, and is suitable for being applied to the fields of high polymer materials, biomedicine, medical devices, sanitary dressings, printing materials, electronic information industry materials, packaging materials, blow molding film forming materials, injection molding products, calendering film forming products, casting stretching products, plastic coating film products, disposable tableware, disposable straws, disposable paper cups and the like.
The above description is only an advantageous embodiment of the present invention, and is not intended to limit the scope of the embodiments of the present invention, and all structural changes made by using the content of the description of the embodiments of the present invention or direct and indirect application to other related technical fields under the inventive concept of the embodiments of the present invention are included in the scope of the embodiments of the present invention.
Claims (19)
1. The degradable cassava acetate starch is characterized by comprising the following raw materials in percentage by weight:
tapioca starch: 35% -37%;
acetic anhydride: 5% -9%;
sodium hydroxide: 3% -5%;
hydrogen peroxide: 0.5 to 1.50 percent;
deionized water: 48% -54.5%;
the above are all the total mass percentages.
2. The degradable cassava acetate starch according to claim 1, wherein the degradable cassava acetate starch comprises the following components by weight:
tapioca starch: 35% -37%;
acetic anhydride: 6.65% -7.35%;
sodium hydroxide: 3.80% -4.20%;
hydrogen peroxide: 0.95 to 1.05 percent;
deionized water: 51% -53%;
the above are all the total mass percentages.
3. The degradable cassava acetate starch according to claim 1, wherein the raw materials further comprise the following components by weight:
sodium hypochlorite: 0 to 1.5 percent;
the above is the total mass percentage.
4. The method for preparing degradable cassava acetate starch according to claim 2, comprising the steps of:
step (1): weighing deionized water and cassava starch according to a formula, sequentially injecting into a container 1, heating and stirring, controlling the temperature within a range of 44-46 ℃, and keeping the temperature and stirring;
step (2): weighing sodium hydroxide according to a formula, diluting with deionized water, dropwise adding into a container 1, and performing alkalization treatment;
and (3): after the step (2) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (4): after the step (3) is finished, additionally taking acetic anhydride, dropwise adding the acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (5): after the step (4), washing powder milk, performing cyclone separation, dehydrating and drying to prepare cassava acetate starch;
the ratio of acetic anhydride in the step (3) to acetic anhydride in the step (4) is 1: 1.
5. The method for preparing degradable cassava acetate starch according to claim 3, comprising the steps of:
step (1): weighing deionized water and cassava starch according to a formula, sequentially injecting into a container 1, heating and stirring, controlling the temperature within a range of 44-46 ℃, and keeping the temperature and stirring;
step (2): weighing sodium hydroxide according to a formula, diluting with deionized water, dropwise adding into a container 1, and performing alkalization treatment;
and (3): after the step (2) is finished, dropwise adding hydrogen peroxide and/or sodium hypochlorite into the container 1 within the temperature range of 44-46 ℃, and continuing to keep the temperature and stir;
and (4): after the step (3) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (5): after the step (4) is finished, dropwise adding acetic anhydride into the container 1 at the temperature of 44-46 ℃, and stirring while keeping the temperature;
and (6): after the step (5), washing powder milk, performing cyclone separation, dehydrating and drying to prepare cassava acetate starch;
the ratio of acetic anhydride in the step (4) to acetic anhydride in the step (5) is 1: 1.
6. The degradable cassava acetate starch resin is characterized by comprising the following raw material components: cassava acetate starch, a plasticizer, a stabilizer, a degrading agent, a cross-linking agent and a lubricating agent;
the plasticizer is one or more of Epoxidized Soybean Oil (ESO), diethyl phthalate (DEP), dimethyl phthalate (DMP), Ethylene Glycol (EG), polyethylene glycol (PEG) and acetyl tributyl citrate (ATBC);
the stabilizer is dimethyl tin mercaptide;
the degradation agent is ethylene glycol;
the cross-linking agent is dicumyl peroxide;
the lubricant is oleamide;
the cassava acetate starch is the cassava acetate starch as set forth in any one of claims 1 to 5.
7. The degradable tapioca acetate starch resin of claim 6, wherein said plasticizer is epoxidized soybean oil.
8. The degradable cassava acetate starch resin according to claim 7, wherein the degradable cassava acetate starch resin comprises the following raw material components:
cassava acetate starch: 67.2-70.7%;
plasticizer epoxidized soybean oil: 25.3-28.8%;
stabilizer dimethyltin mercaptide: 0.3 to 0.5 percent;
the degradation agent is glycol: 1.05 to 1.5 percent
Crosslinking agent dicumyl peroxide: 0.56% -0.8%;
lubricant oleamide: 0.84% -1.2%;
the above are all the total mass percentages.
9. The degradable cassava acetate starch resin according to claim 6, wherein the raw material components further comprise polyvinyl alcohol;
the polyvinyl alcohol is one or more of PVA-1788 polyvinyl alcohol, PVA-2088 polyvinyl alcohol and PVA-2488 polyvinyl alcohol, or PVA-1799 polyvinyl alcohol, PVA-2099 polyvinyl alcohol and PVA-2499 polyvinyl alcohol;
the contents of the raw material components are as follows:
cassava acetate starch: 53.5% -68%;
polyvinyl alcohol: 0 to 14.5 percent;
plasticizer: 23% -26%;
a stabilizer: 0.2 to 0.5 percent;
a degradation agent: 4.5-6.5%;
a crosslinking agent: 0.5 to 0.8 percent;
lubricant: 0.8 to 1.2 percent;
the above are all the total mass percentages.
10. The degradable cassava acetate starch resin according to claim 9,
the method comprises the following steps of (1) obtaining resins with different processing mechanical properties by adjusting the proportion of cassava acetate starch to polyvinyl alcohol in an interactive manner by equivalent amounts of other raw material components, and obtaining the progressive increase of the tensile strength of the resins when the dosage of the polyvinyl alcohol is increased; when the dosage of the cassava acetate starch is increased, the tensile strength of the obtained resin is decreased gradually.
11. The degradable cassava acetate starch resin according to claim 9,
the plasticizer comprises acetyl tributyl citrate (ATBC) and polyethylene glycol (PEG), the proportion range of the acetyl tributyl citrate and the polyethylene glycol is 0.4-1.7, other raw material components are equal, the proportion of the acetyl tributyl citrate (ATBC) and the polyethylene glycol (PEG) are interactively regulated, and different resins with different processing mechanical properties are obtained: when the dosage of the polyethylene glycol is increased, the tensile strength is decreased progressively, and the longitudinal and transverse elongations are increased progressively; when the dosage of the acetyl tributyl citrate is increased, the tensile strength is increased gradually, and the longitudinal and transverse elongations are decreased gradually.
12. The method for preparing the degradable cassava acetate starch resin according to any one of claims 6 to 8, comprising the steps of:
(1) vacuum drying of raw materials: dehydrating and drying the cassava acetate starch in vacuum to a completely anhydrous state;
(2) plasticizing and melting: weighing dried cassava acetate starch and a plasticizer according to a formula, and sequentially putting the cassava acetate starch and the plasticizer into a double-screw mixing mill reactor to be heated, melted and mixed to form a melt A with fluidity;
(3) melting and mixing of an auxiliary agent: weighing a stabilizer, a degrading agent and a cross-linking agent according to a formula, and sequentially adding the stabilizer, the degrading agent and the cross-linking agent into the melt A for melt mixing to form a melt B with fluidity;
(4) melting and mixing of a lubricant: weighing the lubricant according to the formula, and adding the lubricant into the melt B for homogenizing, melting and mixing to obtain a melt C;
(5) and melting and extruding the melt C, and synchronously freezing, sublimating, dehydrating, drying and granulating in the same direction to obtain the degradable cassava acetate starch resin.
13. The method for preparing degradable cassava acetate starch resin according to any one of claims 9 to 11, comprising the steps of:
(1) vacuum drying of raw materials: putting the cassava acetate starch into a vacuum oven for dehydration and drying until the cassava acetate starch is completely anhydrous;
(2) plasticizing and melting: weighing dehydrated and dried cassava acetate starch, a plasticizer and polyvinyl alcohol according to a formula, and sequentially putting the cassava acetate starch, the plasticizer and the polyvinyl alcohol into a double-screw mixing roll reactor to be heated, melted and mixed to form mixed resin with fluidity, so as to obtain a molten mass A;
(3) melting and mixing of an auxiliary agent: weighing a stabilizer, a degrading agent and a cross-linking agent according to a formula, and sequentially adding the stabilizer, the degrading agent and the cross-linking agent into the melt A for melt mixing to form a melt B with fluidity;
(4) melting and mixing of a lubricant: weighing the lubricant according to the formula, and adding the lubricant into the melt B for homogenizing, melting and mixing to obtain a melt C;
(5) and melting and extruding the melt C, synchronously freezing in the same direction, sublimating, dehydrating, drying and granulating to obtain the degradable cassava acetate starch resin.
14. The use of the degradable cassava acetate starch resin according to any one of claims 6 to 11 in the degradable cassava acetate starch resin film, which is characterized by comprising the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): and putting the dehydrated and dried degradable cassava acetate starch resin into a charging barrel of a blow molding machine, and carrying out co-rotating double-screw melting, extrusion, film blowing and traction stretching to obtain a plastic-substituted blown film, namely the degradable cassava acetate starch resin blown film.
15. The use of the degradable cassava acetate starch resin according to any one of claims 6 to 11 in the preparation of a substitute cast stretch plastic film, characterized in that the method comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): melt extrusion casting stretching: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a casting machine for melt extrusion, and performing casting stretching to obtain a 15-100 mu m thick cast stretch film.
16. The use of the degradable cassava acetate starch resin according to any one of claims 6 to 11 in the preparation of a substitute plastic coated product, characterized in that the method comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): coating plastic and spraying film: and extracting the anhydrous degradable cassava acetate starch resin, putting the extracted anhydrous degradable cassava acetate starch resin into a charging barrel of a laminating machine, and carrying out co-rotating double-screw homogeneous melting extrusion coating on the surface of the paper medium to obtain the degradable cassava acetate starch resin plastic-coated laminating product.
17. The use of the degradable cassava acetate starch resin according to any one of claims 6 to 11 in the preparation of a plastic-substituted degradable injection molded product is characterized by comprising the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): injection molding: and extracting the anhydrous degradable cassava acetate starch resin, putting the extracted anhydrous degradable cassava acetate starch resin into a charging barrel of an injection molding machine, carrying out homodromous double-screw homogeneous melting extrusion and compression molding, and preparing the degradable cassava acetate starch resin injection molded product.
18. The use of the degradable cassava acetate starch resin according to any one of claims 6 to 11 in the preparation of a degradable cassava acetate starch film, characterized by comprising the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): melt extrusion casting stretching: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a casting machine for melt extrusion, casting and stretching, and preparing the degradable cassava acetate starch resin film material with the thickness of 200-500 mu m.
19. The use of the degradable cassava acetate starch resin according to any one of claims 6 to 11 in the preparation of a substitute paper printing material, characterized in that it comprises the following steps:
(1): and (3) dehydrating and drying: putting the degradable cassava acetate starch resin into a vacuum oven for dehydration and drying until the degradable cassava acetate starch resin is completely anhydrous, so as to form the degradable cassava acetate starch resin in an anhydrous state;
(2): and (3) melting and quantitative blade coating of a calender: and extracting the anhydrous degradable cassava acetate starch resin, putting the anhydrous degradable cassava acetate starch resin into a charging barrel of a calender for melting and quantitative blade coating, and preparing the degradable cassava acetate starch resin printing material with the thickness of 125-270 mu m.
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