CN112980153A - Full-biodegradable plastic mulching film and preparation method and application thereof - Google Patents
Full-biodegradable plastic mulching film and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
Abstract
The invention provides a full-biodegradable plastic mulching film and a preparation method and application thereof. The components of the full-biodegradable plastic mulching film comprise: 100 parts of full-biodegradable resin, 10-30 parts of auxiliary agent, 10-60 parts of modified starch and 10-100 parts of modified calcium carbonate. The fully biodegradable resin comprises one or more of polybutylene succinate (PBS), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polybutylene adipate-terephthalate (PBAT) and polypropylene carbonate (PPC). The invention can solve the contradiction between the requirement of longer service life of the mulching film for crops, the requirement of lower thickness of the mulching film and the requirement of minimum thickness of the polyethylene plastic mulching film, and simultaneously, the technical scheme of the biodegradable mulching film also has the advantages of slow degradation in the early stage and strong protection capability, and the effect of the biodegradable mulching film on the planting of succeeding crops is reduced by accelerating the degradation in the later stage.
Description
Technical Field
The invention relates to the field of agricultural mulching films, in particular to a full-biodegradable plastic mulching film and a preparation method and application thereof.
Background
China is the most important garlic producing country, consumer country and export country in the world, the export accounts for more than half of the export total of the world, the total planting area is about 1000 ten thousand mu, the planting area is widely distributed, but the area is mainly concentrated in three provinces of Shandong, Henan and Jiangsu, and the planting area of the three provinces accounts for more than 50% of the total area of the whole country.
The garlic likes cold environment condition, the temperature suitable for growth is 12-26 deg.C, the garlic clove can sprout at 3-5 deg.C, the optimum temperature for bulb forming period is 15-20 deg.C. The cold resistance of garlic in the seedling stage is strong, the garlic can tolerate low temperature of-10 ℃ in a short time, the low temperature tolerance is the strongest when 4 to 5 leaves are used, and when the temperature reaches above 26 ℃, the stem leaves begin to wither. The garlic must be subjected to low temperature to produce garlic bulbs, and belongs to plants which must be vernalized by green bodies. After the seedlings are vernalized at low temperature for 30 days, the young seedlings can be differentiated into young garlic shoots and young garlic cloves when meeting the proper temperature, and only single-clove garlic can be produced without vernalization.
Due to the cold and cool taste of garlic and the biological characteristics of having to undergo vernalization, garlic is more suitable for the north, and has to undergo winter overwintering growth in winter, and the requirements on the sowing time are strict: too early seeding, big seedling, vigorous growth, excessive nutrient consumption and reduced cold tolerance; late sowing, small seedlings, less accumulated nutrients of the seedlings, shallow roots and poor cold resistance. Therefore, in the main garlic producing place, the sowing time of garlic is most concentrated in the upper ten days of 9 to 10 months per year.
The yield increasing and income increasing function of the mulching film on the ground during the garlic production is accepted by farmers and becomes a conventional garlic planting technology. Particularly, in major garlic producing areas such as Shandong and Henan, the garlic mulching film cultivation area is more than 85 percent. The mulching film has the following functions:
the environmental conditions are improved. After the mulching film is covered, the surface temperature of soil can be increased by 2-3 ℃ before winter, the growth of garlic seedlings before winter can be accelerated, the garlic seedlings are strong, the cold resistance is strong, and the low-temperature freezing death rate during overwintering is greatly reduced; the coated garlic has early green turning, fast growth, great plant growth amount and great leaf area, and lays the foundation for high yield.
After the mulching film is covered, the water retention and fertility preservation of the soil are enhanced, the nutrient utilization rate is improved, the soil is kept loose, the ground hardening caused by excessive watering is prevented, and the soil environment condition is effectively improved.
The garlic film also reduces the occurrence of plant diseases and insect pests. The mulching film prevents the seed flies from laying eggs around the garlic roots, and reduces root maggots. The mulching also inhibits the occurrence and harm of weeds.
After the garlic is cultivated by mulching, the bolting period and the maturation period can be advanced. The precocity not only can increase the income of the garlic on the market in advance, but also can create conditions for the precocity and can effectively adjust the cultivation period of the next crop.
As can be seen from the above, in order to increase the yield and income of garlic, the action period of garlic film covering is from 9 months at the bottom of the first year to 10 months at the next year after the temperature rises, generally from 4 months to 5 months, and about 6 months before and after the garlic is harvested after sowing.
Mulching film mulching is one of the conventional technologies for garlic planting, but has more special requirements on mulching film planting: when garlic producers plant garlic, garlic seeds are evenly stacked in the soil, covered with the soil and then covered with a film, garlic buds burst the mulching film after the garlic sprouts to come out of the soil, and a small amount of garlic buds which cannot burst the mulching film are ejected out by manual assistance. The mulching film around garlic buds can be damaged by artificial auxiliary seedling emergence, the pest raising effect of the mulching film is degraded, and the garlic overwintering protection effect is realized. According to the experience of garlic producers, the garlic is planted by adopting the traditional polyethylene mulching film, the thickness of the mulching film is most suitable to be about 0.005 mm, and garlic buds can hardly burst the mulching film with the thickness.
However, the polyethylene mulching film with the thickness of 0.005 mm does not meet the national standard and belongs to the prohibited use mulching film. The thickness standard of the polyethylene mulching film is improved to 0.010 mm according to the specification of polyethylene blow molding ground covering agricultural films implemented in 2018 in China, the polyethylene mulching film meeting the national standard cannot be used for producing garlic, and the contradiction exists between the polyethylene mulching film standard and the garlic film covering agricultural requirements.
The appearance of the biodegradable mulching film provides a possible way for solving the contradiction. According to the national standard "full biodegradable agricultural mulch films", biodegradable mulch films do not specify a minimum thickness of the mulch film, allowing production and use of mulch films below 0.010 mm. The main defect of the existing biodegradable mulching film in garlic production is that the degradation period of the existing biodegradable mulching film is shorter than the growth period of garlic, namely after garlic is planted in the mulching film, the strength and the elongation of the mulching film are reduced due to degradation in the garlic growth process, cracks, broken holes and the like occur, and even partial film-free is generated in severe cases, so that the protective capacity of the garlic is lost, and the yield and the income are reduced. Problems with garlic mulch can also occur on some other crops, such as crops of underground-grown roots, tubers or fruits of peanuts, potatoes, sweet potatoes, and the like.
In order to obtain the biodegradable mulching films with different degradation periods, biodegradable plastics with different degradation periods are adopted, and starch which can be decomposed by microorganisms with different contents is added to obtain the expected biodegradable mulching films. However, the degradation period of the biodegradable plastic is obviously longer than the growth period of crops, and the addition of the starch reduces the mechanical strength and the water resistance of the mulching film, and causes poor constructability and unexpected early cracking of the mulching film, thereby affecting the practicability of the mulching film and being not suitable for large-scale popularization.
The problems of garlic mulching planting also exist in other crops, for example, northern spring peanuts are basically covered by a mulching film, the main function of the mulching film is to improve the ground temperature in spring and promote the growth of the peanuts in seedling stage, meanwhile, the growth season of the peanuts, namely the spring and summer season, is also a season with high occurrence of weeds, and the peanut mulching film can greatly reduce the occurrence of weeds and reduce the use of herbicides.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a full-biodegradable plastic mulching film, which is a technical solution of the biodegradable mulching film formed for solving the problems that the crops need a longer mulching film life, the mulching film thickness is required to be lower and the use of the ultrathin polyethylene plastic mulching film is forbidden.
In order to achieve the above object, in a first aspect, the present invention provides a fully biodegradable plastic mulch film, comprising: 100 parts of full-biodegradable resin, 10-30 parts of auxiliary agent, 10-60 parts of modified starch and 10-100 parts of modified calcium carbonate.
Optionally, the fully biodegradable resin includes one or more of polybutylene succinate (PBS), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polybutylene adipate-terephthalate (PBAT), and polypropylene carbonate (PPC).
Optionally, the auxiliaries include one or a combination of plasticizers, nucleating agents, chain extenders, opening agents, lubricants, antiblocking agents, antistatic agents, light absorbers, or antioxidants.
Optionally, the preparation method of the modified starch comprises the following steps: (1) paste mixing: adding starch raw materials into sodium hydroxide alkaline solution with the pH value of 8-9, mixing and stirring the mixture to form starch slurry, heating the starch slurry to 80-90 ℃ to form pasty starch slurry, wherein the mass concentration of starch in the starch slurry is 50-80%; (2) modification reaction: adding 10 parts of toluene diisocyanate and ethylene-vinyl acetate copolymer mixed emulsion, 0.2-1 part of stannous octoate and 2-4 parts of polyvinyl alcohol aqueous solution into 100 parts of pasty starch slurry according to the weight ratio, and then reacting at 75-105 ℃ for 10-20h to obtain modified starch slurry; wherein the mass ratio of the toluene diisocyanate to the ethylene-vinyl acetate copolymer is 1: 0.2-1, and the mass concentration of the emulsion is 20-40%; the mass concentration of the polyvinyl alcohol aqueous solution is 10-20%; (3) and (3) post-treatment: and drying, grinding and screening the modified starch slurry to obtain the modified starch.
Optionally, the starch raw material is one or a combination of potato starch, corn starch, wheat starch and tapioca starch.
Optionally, the components further comprise plant straw fibers, and the plant straw fibers are one or a combination of bamboo fibers, wood fibers or hemp fibers.
Optionally, the preparation method of the modified treated calcium carbonate comprises the following steps: (1) weighing 100 parts of nano calcium carbonate powder by mass, dispersing the nano calcium carbonate powder in an ethanol water solution, adding 10 parts of an absolute ethanol solution of a composite coupling agent with the concentration of 20 wt%, continuously stirring and heating for 1-2h in a high-speed stirrer at the rotation speed of 1000-; wherein the components of the composite coupling agent are aluminum zirconate coupling agent, gamma-methacryloxypropyl trimethoxy silane and titanate coupling agent, and the weight ratio is 1:1: 1; (2) adding primary treated calcium carbonate powder, sodium silicate and deionized water into a reaction bottle, slowly adding 2.5 wt% of mixed solution of hydrochloric acid and oxalic acid to ensure that the pH value of the system is 6.9-7.0, and grinding in a grinder to obtain silica sol coated calcium carbonate powder, wherein the mass ratio of hydrochloric acid to oxalic acid is 1: 1; (3) sequentially adding hydroxyethyl methacrylate, polycaprolactone diol, toluene diisocyanate and stannous octoate into the calcium carbonate powder coated by the silica sol, uniformly stirring, reacting for 5-6 hours in a sealed high-pressure kettle under the conditions of keeping stirring and controlling the temperature to be 95-105 ℃, and drying at the temperature of 100 ℃ in vacuum for 120 ℃ to obtain modified calcium carbonate; wherein the mass ratio of the hydroxyl methacrylate to the polycaprolactone diol to the toluene diisocyanate to the stannous octoate is 10:2:15: 0.1.
In order to achieve the above object, in a second aspect, the present invention provides a method for preparing a fully biodegradable plastic mulch film, comprising the steps of: (1) mixing 10-60 parts of modified starch and 80-100 parts of modified calcium carbonate in a ball mill according to a weight ratio, adding 10 parts of ethanol water solution and 1 part of citric acid, grinding at the temperature of 80-100 ℃ for 1-2 hours, and drying to obtain a starch/calcium carbonate composite filler; (2) weighing raw materials comprising the starch/calcium carbonate composite filler, 100 parts of full-biodegradable resin and 10-30 parts of auxiliary agent according to a weight ratio, adding the raw materials into a mixing hopper according to a set proportion, uniformly stirring, feeding the mixture into a single-screw extruder with an exhaust function, melting and plasticizing at the temperature of 150-220 ℃, exhausting, extruding and feeding the mixture into a runner of a die head; (3) the raw materials are melted and extruded into a die head with the temperature of 180-220 ℃, and then are cooled at the temperature of 60-65 ℃ by a cooling roller to form a thick sheet; (4) the cooled thick sheet is subjected to longitudinal and transverse successive stretching or longitudinal and transverse synchronous stretching; (5) the stretched membrane enters a traction station, and is rolled into a biodegradable full-biodegradable plastic mulching film with the thickness of 4-15um in a rolling machine through post-treatment processes such as edge cutting, thickness measurement, corona treatment and the like.
Optionally, the raw material components further include plant straw fiber, and the plant straw fiber is one or a combination of bamboo fiber, wood fiber or hemp fiber.
In order to achieve the above objects, in a third aspect, the present invention provides an application of a full biodegradable plastic mulching film applied to garlic, peanuts, eggplants, corns, watermelons, rice or tobacco seedlings.
The invention has the following beneficial effects:
(1) according to the fully-biodegradable mulching film disclosed by the invention, the modified calcium carbonate and-OH-NCO groups grafted and coated on the surface of the starch react with each other to form a good interface bonding to form a composite reinforcing filler, so that the addition range of fillers such as the starch and the calcium carbonate can be greatly enlarged, and particularly, the mechanical strength of the mulching film is not greatly influenced due to the overlarge addition range of the starch.
(2) The mulching film is different from the prior art in mild degradation, but has small intensity change in the early degradation stage and a relatively stable intensity plateau stage, and after a certain degradation degree is reached, the intensity can be rapidly reduced to enable the mulching film to be broken into small blocks, so that the good coverage characteristic can be successfully maintained in the crop growth period, and when crops are harvested and land is tidied, the crop harvesting and the next planting are not influenced.
(3) The technical effect is realized because the raw material treatment and preparation method of the invention can realize that the fillers, the matrix and the fillers have good dispersibility and interface bonding property, and molecular chains of various substances are mutually crossed, so that a good cross-linked network is still maintained after starch is firstly hydrolyzed or degraded, and only after enough starch is firstly decomposed and the degradation degree of biodegradable resin reaches a certain degree, the mechanical strength of the mulching film can be sharply reduced, and the mulching film is finally cracked and dispersed in soil for subsequent further degradation, thereby not influencing crops and soil.
(4) The biodegradable mulching film is used for planting crops needing to be coated, for example, garlic, peanuts, eggplants and other crops, and due to the characteristic of quick later-stage degradation of the technical scheme, the remaining time of the residual mulching film in soil can be shortened, and the planting of the succeeding crops is facilitated.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a test graph of tensile strength of the inventive fully biodegradable plastic film as a function of natural time.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The invention relates to a full-biodegradable plastic mulching film, which comprises the following components: 100 parts of full-biodegradable resin, 10-30 parts of auxiliary agent, 10-60 parts of modified starch and 10-100 parts of modified calcium carbonate. The fully biodegradable resin comprises one or more of polybutylene succinate (PBS), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polybutylene adipate-terephthalate (PBAT) and polypropylene carbonate (PPC). The auxiliary agent comprises one or a combination of a plasticizer, a nucleating agent, a chain extender, an opening agent, a lubricant, an anti-blocking agent, an antistatic agent, a light absorber or an antioxidant.
In the fully biodegradable plastic mulching film according to the present invention, the preparation method of the modified starch comprises the steps of: (1) paste mixing: adding starch raw materials into sodium hydroxide alkaline solution with the pH value of 8-9, mixing and stirring the mixture to form starch slurry, heating the starch slurry to 80-90 ℃ to form pasty starch slurry, wherein the mass concentration of starch in the starch slurry is 50-80%; (2) modification reaction: adding 10 parts of toluene diisocyanate and ethylene-vinyl acetate copolymer mixed emulsion, 0.2-1 part of stannous octoate and 2-4 parts of polyvinyl alcohol aqueous solution into 100 parts of pasty starch slurry according to the weight ratio, and then reacting at 75-105 ℃ for 10-20h to obtain modified starch slurry; wherein the mass ratio of the toluene diisocyanate to the ethylene-vinyl acetate copolymer is 1: 0.2-1, and the mass concentration of the emulsion is 20-40%; the mass concentration of the polyvinyl alcohol aqueous solution is 10-20%; (3) and (3) post-treatment: and drying, grinding and screening the modified starch slurry to obtain the modified starch. The starch raw material is one or a combination of potato starch, corn starch, wheat starch or cassava starch.
In the fully biodegradable plastic mulching film, the components further comprise plant straw fibers, and the plant straw fibers are one or a combination of bamboo fibers, wood fibers or hemp fibers.
In the fully biodegradable plastic mulching film according to the invention, the preparation method of the modified calcium carbonate comprises the following steps: (1) weighing 100 parts of nano calcium carbonate powder by mass, dispersing the nano calcium carbonate powder in an ethanol water solution, adding 10 parts of an absolute ethanol solution of a composite coupling agent with the concentration of 20 wt%, continuously stirring and heating for 1-2h in a high-speed stirrer at the rotation speed of 1000-; wherein the components of the composite coupling agent are aluminum zirconate coupling agent, gamma-methacryloxypropyl trimethoxy silane and titanate coupling agent, and the weight ratio is 1:1: 1; (2) adding primary treated calcium carbonate powder, sodium silicate and deionized water into a reaction bottle, slowly adding a mixed solution of 2.5 wt% hydrochloric acid and oxalic acid to ensure that the pH value of the system is 6.9-7.0, and grinding in a grinder to obtain silica sol coated calcium carbonate powder, wherein the mass ratio of hydrochloric acid to oxalic acid is 1: 1; (3) sequentially adding hydroxyethyl methacrylate, polycaprolactone diol, toluene diisocyanate and stannous octoate into the calcium carbonate powder coated by the silica sol, uniformly stirring, reacting for 5-6 hours in a sealed high-pressure kettle under the conditions of keeping stirring and controlling the temperature to be 95-105 ℃, and drying at the temperature of 100 ℃ in vacuum for 120 ℃ to obtain modified calcium carbonate; wherein the mass ratio of the hydroxyl methacrylate to the polycaprolactone diol to the toluene diisocyanate to the stannous octoate is 10:2:15: 0.1.
The preparation method of the full-biodegradable plastic mulching film comprises the following steps: mixing 10-60 parts of modified starch and 80-100 parts of modified calcium carbonate in a ball mill according to a weight ratio, adding 10 parts of ethanol aqueous solution and 1 part of citric acid, grinding at the temperature of 80-100 ℃ for 1-2 hours, and drying to obtain a starch/calcium carbonate composite filler; (2) weighing raw materials comprising the starch/calcium carbonate composite filler, 100 parts of full-biodegradable resin and 10-30 parts of auxiliary agent according to a weight ratio, adding the raw materials into a mixing hopper according to a set proportion, uniformly stirring, feeding the mixture into a single-screw extruder with an exhaust function, melting and plasticizing at the temperature of 150-220 ℃, exhausting, extruding and feeding the mixture into a runner of a die head; (3) the raw materials are melted and extruded into a die head with the temperature of 180-220 ℃, and then are cooled at the temperature of 60-65 ℃ by a cooling roller to form a thick sheet; (4) the cooled thick sheet is subjected to longitudinal and transverse successive stretching or longitudinal and transverse synchronous stretching; (5) the stretched membrane enters a traction station, and is rolled into a biodegradable full-biodegradable plastic mulching film with the thickness of 4-15um in a rolling machine through post-treatment processes such as edge cutting, thickness measurement, corona treatment and the like.
In the preparation method of the full-biodegradable plastic mulching film, the raw material components further comprise plant straw fibers, and the plant straw fibers are one or a combination of bamboo fibers, wood fibers or hemp fibers.
The full-biodegradable plastic mulching film can be applied to garlic, peanuts, eggplants, corns, watermelons, rice or tobacco seedlings.
The fully biodegradable plastic mulch film of the present invention will be specifically described with reference to specific examples.
Example 1
Preparing modified starch:
(1) paste mixing: adding a corn starch raw material into a sodium hydroxide alkaline solution with the pH value of 8, mixing and stirring to form starch slurry, and heating to 80 ℃ to form pasty starch slurry, wherein the mass concentration of starch in the starch slurry is 50%;
(2) modification reaction: adding 10 parts of toluene diisocyanate and ethylene-vinyl acetate copolymer mixed emulsion, 0.2 part of stannous octoate and 2 parts of polyvinyl alcohol aqueous solution into 100 parts of pasty starch slurry according to the weight ratio, and then reacting at 75 ℃ for 10 hours to obtain modified starch slurry; wherein the mass ratio of the toluene diisocyanate to the ethylene-vinyl acetate copolymer is 1: 0.2-1, and the mass concentration of the emulsion is 20%; the mass concentration of the polyvinyl alcohol aqueous solution is 10%;
(3) and (3) post-treatment: and drying, grinding and screening the modified starch slurry to obtain the modified starch.
(II) preparing modified calcium carbonate:
(1) weighing 100 parts of nano calcium carbonate powder by weight, dispersing the nano calcium carbonate powder in an ethanol water solution, adding 10 parts of an absolute ethanol solution of a composite coupling agent with the concentration of 20 wt%, continuously stirring and heating for 1h in a high-speed stirrer at the rotation speed of 1000 revolutions per minute and the temperature of 70 ℃, filtering, and drying at 100 ℃ to obtain primary treated calcium carbonate powder; wherein the components of the composite coupling agent are aluminum zirconate coupling agent, gamma-methacryloxypropyl trimethoxy silane and titanate coupling agent, and the weight ratio is 1:1: 1;
(2) adding primary treated calcium carbonate powder, sodium silicate and deionized water into a reaction bottle, slowly adding a mixed solution of 2.5 wt% hydrochloric acid and oxalic acid to ensure that the pH value of the system is 6.9, and grinding in a grinder to obtain silica sol coated calcium carbonate powder, wherein the mass ratio of hydrochloric acid to oxalic acid is 1: 1;
(3) sequentially adding hydroxyethyl methacrylate, polycaprolactone diol, toluene diisocyanate and stannous octoate into the calcium carbonate powder coated by the silica sol, uniformly stirring, reacting for 5 hours in a sealed high-pressure kettle under the conditions of keeping stirring and controlling the temperature to be 95 ℃, and drying at the temperature of 100 ℃ in vacuum to obtain modified calcium carbonate; wherein the mass ratio of the hydroxyl methacrylate to the polycaprolactone diol to the toluene diisocyanate to the stannous octoate is 10:2:15: 0.1.
(III) preparing a full-biodegradable plastic mulching film:
(1) mixing 10 parts of modified starch and 80 parts of modified calcium carbonate in a ball mill according to a weight ratio, adding 10 parts of ethanol aqueous solution and 1 part of citric acid, grinding for 1 hour at the temperature of 80 ℃, and drying to obtain a starch/calcium carbonate composite filler;
(2) weighing raw materials comprising the starch/calcium carbonate composite filler, 100 parts of polybutylene adipate-butylene terephthalate (PBAT) and 10 parts of auxiliary agent according to a set proportion by weight, adding the raw materials into a mixing hopper, uniformly stirring, feeding the mixture into a single-screw extruder with an exhaust function, melting and plasticizing at the temperature of 150 ℃, exhausting, extruding and feeding the mixture into a runner of a die head;
(3) the raw materials are melted and extruded into a die head with the temperature of 180 ℃, and then are cooled at the temperature of 60 ℃ by a cooling roller to form a thick sheet;
(4) the cooled thick sheet is subjected to longitudinal and transverse successive stretching or longitudinal and transverse synchronous stretching;
(5) the stretched membrane enters a traction station, and is rolled into a biodegradable full-biodegradable plastic mulching film with the thickness of 4um in a rolling machine through the post-treatment processes of edge cutting, thickness measurement, corona treatment and the like, so as to be used for planting garlic.
Example 2
Preparing modified starch:
(1) paste mixing: adding potato starch raw material into sodium hydroxide alkaline solution with pH of 8.5, mixing and stirring to obtain starch slurry, heating to 85 deg.C to obtain pasty starch slurry with starch mass concentration of 60%;
(2) modification reaction: adding 10 parts of toluene diisocyanate and ethylene-vinyl acetate copolymer mixed emulsion, 0.6 part of stannous octoate and 3 parts of polyvinyl alcohol aqueous solution into 100 parts of pasty starch slurry according to the weight ratio, and then reacting at 90 ℃ for 15 hours to obtain modified starch slurry; wherein the mass ratio of the toluene diisocyanate to the ethylene-vinyl acetate copolymer is 1: 0.2-1, and the mass concentration of the emulsion is 30%; the mass concentration of the polyvinyl alcohol aqueous solution is 15%;
(3) and (3) post-treatment: and drying, grinding and screening the modified starch slurry to obtain the modified starch.
(II) preparing modified calcium carbonate:
(1) weighing 100 parts of nano calcium carbonate powder by mass, dispersing the nano calcium carbonate powder in an ethanol water solution, adding 10 parts of an absolute ethanol solution of a composite coupling agent with the concentration of 20 wt%, continuously stirring and heating for 1-2h in a high-speed stirrer at the rotating speed of 1500 rpm and the temperature of 75 ℃, filtering, and drying at 110 ℃ to obtain primary treated calcium carbonate powder; wherein the components of the composite coupling agent are aluminum zirconate coupling agent, gamma-methacryloxypropyl trimethoxy silane and titanate coupling agent, and the weight ratio is 1:1: 1;
(2) adding primary treated calcium carbonate powder, sodium silicate and deionized water into a reaction bottle, slowly adding a mixed solution of 2.5 wt% hydrochloric acid and oxalic acid to ensure that the pH value of the system is 7.0, and grinding in a grinder to obtain silica sol coated calcium carbonate powder, wherein the mass ratio of hydrochloric acid to oxalic acid is 1: 1;
(3) sequentially adding hydroxyethyl methacrylate, polycaprolactone diol, toluene diisocyanate and stannous octoate into the calcium carbonate powder coated by the silica sol, uniformly stirring, reacting for 5.5 hours in a sealed high-pressure kettle under the conditions of keeping stirring and controlling the temperature to be 100 ℃, and drying at the temperature of 110 ℃ in vacuum to obtain modified calcium carbonate; wherein the mass ratio of the hydroxyl methacrylate to the polycaprolactone diol to the toluene diisocyanate to the stannous octoate is 10:2:15: 0.1.
(III) preparing a full-biodegradable plastic mulching film:
(1) mixing 40 parts of modified starch and 90 parts of modified calcium carbonate in a ball mill according to a weight ratio, adding 10 parts of ethanol aqueous solution and 1 part of citric acid, grinding for 1.5 hours at the temperature of 90 ℃, and drying to obtain a starch/calcium carbonate composite filler;
(2) weighing raw materials comprising the starch/calcium carbonate composite filler, 100 parts of polybutylene succinate (PBS), 20 parts of bamboo fiber and 20 parts of auxiliary agent according to a set proportion by weight, adding the raw materials into a mixing hopper, uniformly stirring, feeding the raw materials into a single-screw extruder with an exhaust function, melting and plasticizing at 190 ℃, exhausting, and extruding the mixture into a flow channel of a die head;
(3) the raw materials are melted and extruded into a die head with the temperature of 190 ℃, and then are cooled at the temperature of 63 ℃ by a cooling roller to form a thick sheet;
(4) the cooled thick sheet is subjected to longitudinal and transverse successive stretching or longitudinal and transverse synchronous stretching;
(5) the stretched membrane enters a traction station, and is rolled into a biodegradable full-biodegradable plastic mulching film with the thickness of 8um in a rolling machine through the post-treatment processes of edge cutting, thickness measurement, corona treatment and the like, so as to be used for planting garlic.
Example 3
Preparing modified starch:
(1) paste mixing: adding a cassava starch raw material into an alkaline solution of sodium hydroxide with the pH value of 9, mixing and stirring to form starch slurry, heating to 90 ℃ to form pasty starch slurry, wherein the mass concentration of starch in the starch slurry is 80%;
(2) modification reaction: adding 10 parts of toluene diisocyanate and ethylene-vinyl acetate copolymer mixed emulsion, 1 part of stannous octoate and 4 parts of polyvinyl alcohol aqueous solution into 100 parts of pasty starch slurry according to the weight ratio, and then reacting at 105 ℃ for 20 hours to obtain modified starch slurry; wherein the mass ratio of the toluene diisocyanate to the ethylene-vinyl acetate copolymer is 1: 0.2-1, and the mass concentration of the emulsion is 40%; the mass concentration of the polyvinyl alcohol aqueous solution is 20%;
(3) and (3) post-treatment: and drying, grinding and screening the modified starch slurry to obtain the modified starch.
(II) preparing modified calcium carbonate:
(1) weighing 100 parts of nano calcium carbonate powder by mass, dispersing the nano calcium carbonate powder in an ethanol water solution, adding 10 parts of an absolute ethanol solution of a composite coupling agent with the concentration of 20 wt%, continuously stirring and heating for 1-2h in a high-speed stirrer at the rotating speed of 2000 r/min and the temperature of 80 ℃, filtering, and drying at 120 ℃ to obtain primary treated calcium carbonate powder; wherein the components of the composite coupling agent are aluminum zirconate coupling agent, gamma-methacryloxypropyl trimethoxy silane and titanate coupling agent, and the weight ratio is 1:1: 1;
(2) adding primary treated calcium carbonate powder, sodium silicate and deionized water into a reaction bottle, slowly adding a mixed solution of 2.5 wt% hydrochloric acid and oxalic acid to ensure that the pH value of the system is 7.0, and grinding in a grinder to obtain silica sol coated calcium carbonate powder, wherein the mass ratio of hydrochloric acid to oxalic acid is 1: 1;
(3) sequentially adding hydroxyethyl methacrylate, polycaprolactone diol, toluene diisocyanate and stannous octoate into the calcium carbonate powder coated by the silica sol, uniformly stirring, reacting for 6 hours in a sealed high-pressure kettle under the conditions of keeping stirring and controlling the temperature to be 105 ℃, and drying at the temperature of 120 ℃ in vacuum to obtain modified calcium carbonate; wherein the mass ratio of the hydroxyl methacrylate to the polycaprolactone diol to the toluene diisocyanate to the stannous octoate is 10:2:15: 0.1.
(III) preparing a full-biodegradable plastic mulching film:
(1) mixing 60 parts of modified starch and 100 parts of modified calcium carbonate in a ball mill according to a weight ratio, adding 10 parts of ethanol water solution and 1 part of citric acid, grinding for 2 hours at the temperature of 100 ℃, and drying to obtain a starch/calcium carbonate composite filler;
(2) weighing raw materials comprising the starch/calcium carbonate composite filler, 100 parts of Polyhydroxyalkanoate (PHA) and 30 parts of an auxiliary agent according to a set proportion by weight, adding the raw materials into a mixing hopper, uniformly stirring, feeding the mixture into a single-screw extruder with an exhaust function, melting and plasticizing at 220 ℃, exhausting, extruding and feeding the mixture into a runner of a die head;
(3) the raw materials are melted and extruded into a die head with the temperature of 220 ℃, and then are cooled at the temperature of 65 ℃ by a cooling roller to form a thick sheet;
(4) the cooled thick sheet is subjected to longitudinal and transverse successive stretching or longitudinal and transverse synchronous stretching;
(5) the stretched film enters a traction station, and is rolled into a biodegradable full-biodegradable plastic mulching film with the thickness of 15um in a rolling machine through the post-treatment processes of edge cutting, thickness measurement, corona treatment and the like, so as to be used for planting garlic.
Example 4
The same procedure as in example 2 was repeated, except that wheat starch was used in place of potato starch and hemp fiber was used in place of bamboo fiber.
Comparative example 1
The procedure was as in example 1 except that the starch was not modified.
Comparative example 2
The procedure was as in example 1 except that the calcium carbonate was not modified.
Comparative example 3
The same procedure as in example 1 was repeated except that the calcium carbonate and the starch were not modified.
Comparative example 4
The modified starch and the modified calcium carbonate are not prepared into the starch/calcium carbonate composite filler in advance, and are directly added into the raw materials for subsequent processing, and other parts are the same as those in the embodiment 1.
It is noted that the additives of the above examples and comparative examples are the same in kind and combination, and mainly consist of the plasticizer dibutyl sebacate and the antioxidant 1010 in 10 and 1 parts.
And (3) performance testing:
1. measurement of tensile Strength and elongation at Break
According to the test conditions for films and sheets, part 3 of the national Standard "determination of tensile Properties of plastics" (GB \ T1040.3-2006): the dumbbell specimens have a length of 150mm, a narrow parallel width of 10mm, a drawing speed of 200mm/min and a room temperature of 25 ℃.
2. Determination of Right Angle tear Strength
Quote QB/T1130-1991 "Plastic Right Angle tear Performance test method", tensile speed 200mm/min, room temperature 25 ℃.
The results of the performance tests on the products obtained in the above examples and comparative examples are shown in the following table:
3. tensile Strength testing of the Membrane in the biodegradation cycle
The same mulching film is placed outdoors in the region of Jinxiang county in Shandong province, the natural aging time period is 10 months and 1 day to the next year, 5 months and 30 days, the 10 months and 1 day are used as the 1 st sampling time, and the sampling is carried out once every 0.5 month for 17 times.
According to the test conditions for films and sheets, part 3 of the national Standard "determination of tensile Properties of plastics" (GB \ T1040.3-2006): the dumbbell-shaped bars had a length of 150mm, a narrow parallel width of 10mm and a drawing speed of 200 mm/min.
Fig. 1 shows a test graph of tensile strength of the inventive fully biodegradable plastic film as a function of natural time. Wherein, the ordinate is the longitudinal tensile strength in MPa; the abscissa is the sequential point of sampling at 0.5 month intervals.
Through the above embodiments, it can be seen that the tensile strength, elongation at break and tear strength of the mulching film are greatly affected by the fully biodegradable plastic film provided by the invention, the modified starch, the modified calcium carbonate and the advanced composite treatment mode of the modified starch and the modified calcium carbonate. In addition, the mulching film is different from the prior art that the biodegradable mulching film is slowly degraded, the strength change in the early degradation period is small, a relatively stable strength plateau period is provided, and after a certain degradation degree is reached, the strength can be rapidly reduced to enable the mulching film to be broken into small pieces, so that the good coverage characteristic can be successfully maintained in the crop growth period, when the crops are harvested and land is cleared, the crop harvesting and the next planting are not influenced, and the biodegradable mulching film of the embodiment is suitable for planting garlic in Jinxiang counties in Shandong. Although some specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the above illustration is only for the purpose of illustration and is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Although some specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the above illustration is only for the purpose of illustration and is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The full-biodegradable plastic mulching film is characterized by comprising the following components: 100 parts of full-biodegradable resin, 10-30 parts of auxiliary agent, 10-60 parts of modified starch and 10-100 parts of modified calcium carbonate.
2. The fully biodegradable plastic mulch of claim 1, wherein the fully biodegradable resin comprises one or more of polybutylene succinate (PBS), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polybutylene adipate terephthalate (PBAT), polypropylene carbonate (PPC).
3. The fully biodegradable plastic mulch film according to claim 1, wherein the adjuvant comprises one or a combination of plasticizers, nucleating agents, chain extenders, opening agents, lubricants, anti-blocking agents, antistatic agents, light absorbers or antioxidants.
4. The fully biodegradable plastic mulch film according to claim 1, wherein the preparation method of the modified starch comprises the steps of:
(1) paste mixing: adding starch raw materials into sodium hydroxide alkaline solution with the pH value of 8-9, mixing and stirring the mixture to form starch slurry, heating the starch slurry to 80-90 ℃ to form pasty starch slurry, wherein the mass concentration of starch in the starch slurry is 50-80%;
(2) modification reaction: adding 10 parts of toluene diisocyanate and ethylene-vinyl acetate copolymer mixed emulsion, 0.2-1 part of stannous octoate and 2-4 parts of polyvinyl alcohol aqueous solution into 100 parts of pasty starch slurry according to the weight ratio, and then reacting at 75-105 ℃ for 10-20h to obtain modified starch slurry; wherein the mass ratio of the toluene diisocyanate to the ethylene-vinyl acetate copolymer is 1: 0.2-1, and the mass concentration of the emulsion is 20-40%; the mass concentration of the polyvinyl alcohol aqueous solution is 10-20%;
(3) and (3) post-treatment: and drying, grinding and screening the modified starch slurry to obtain the modified starch.
5. The fully biodegradable plastic mulch film according to claim 4 wherein the starch material is one or a combination of potato starch, corn starch, wheat starch or tapioca starch.
6. The fully biodegradable plastic mulch film according to claim 1, wherein the components further comprise plant straw fibers, wherein the plant straw fibers are one or a combination of bamboo fibers, wood fibers or hemp fibers.
7. The fully biodegradable plastic mulch according to claims 1-6 wherein the preparation method of the modified treated calcium carbonate comprises the following steps:
(1) weighing 100 parts of nano calcium carbonate powder by mass, dispersing the nano calcium carbonate powder in an ethanol water solution, adding 10 parts of an absolute ethanol solution of a composite coupling agent with the concentration of 20 wt%, continuously stirring and heating for 1-2h in a high-speed stirrer at the rotation speed of 1000-; wherein the components of the composite coupling agent are aluminum zirconate coupling agent, gamma-methacryloxypropyl trimethoxy silane and titanate coupling agent, and the weight ratio is 1:1: 1;
(2) adding primary treated calcium carbonate powder, sodium silicate and deionized water into a reaction bottle, slowly adding 2.5 wt% of mixed solution of hydrochloric acid and oxalic acid to ensure that the pH value of the system is 6.9-7.0, and grinding in a grinder to obtain silica sol coated calcium carbonate powder, wherein the mass ratio of hydrochloric acid to oxalic acid is 1: 1;
(3) sequentially adding hydroxyethyl methacrylate, polycaprolactone diol, toluene diisocyanate and stannous octoate into the calcium carbonate powder coated by the silica sol, uniformly stirring, reacting for 5-6 hours in a sealed high-pressure kettle under the conditions of keeping stirring and controlling the temperature to be 95-105 ℃, and drying at the temperature of 100 ℃ in vacuum for 120 ℃ to obtain modified calcium carbonate; wherein the mass ratio of the hydroxyl methacrylate to the polycaprolactone diol to the toluene diisocyanate to the stannous octoate is 10:2:15: 0.1.
8. The preparation method of the full-biodegradable plastic mulching film of claims 1-7 is characterized by comprising the following steps:
(1) mixing 10-60 parts of modified starch and 80-100 parts of modified calcium carbonate in a ball mill according to a weight ratio, adding 10 parts of ethanol water solution and 1 part of citric acid, grinding at the temperature of 80-100 ℃ for 1-2 hours, and drying to obtain a starch/calcium carbonate composite filler;
(2) weighing raw materials comprising the starch/calcium carbonate composite filler, 100 parts of full-biodegradable resin and 10-30 parts of auxiliary agent according to a weight ratio, adding the raw materials into a mixing hopper according to a set proportion, uniformly stirring, feeding the mixture into a single-screw extruder with an exhaust function, melting and plasticizing at the temperature of 150-220 ℃, exhausting, extruding and feeding the mixture into a runner of a die head;
(3) the raw materials are melted and extruded into a die head with the temperature of 180-220 ℃, and then are cooled at the temperature of 60-65 ℃ by a cooling roller to form a thick sheet;
(4) the cooled thick sheet is subjected to longitudinal and transverse successive stretching or longitudinal and transverse synchronous stretching;
(5) the stretched membrane enters a traction station, and is rolled into a biodegradable full-biodegradable plastic mulching film with the thickness of 4-15um in a rolling machine through post-treatment processes such as edge cutting, thickness measurement, corona treatment and the like.
9. The method for preparing full biodegradable plastic mulching film according to claim 8, wherein the raw material components further comprise plant straw fibers, and the plant straw fibers are one or a combination of bamboo fibers, wood fibers or hemp fibers.
10. Use of a fully biodegradable plastic mulch film according to any one of claims 1-9 wherein, in garlic, peanut, eggplant, corn, watermelon, rice or tobacco seedlings.
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Application publication date: 20210618 |