CN111205603B - Biodegradable mulching film and preparation method thereof - Google Patents
Biodegradable mulching film and preparation method thereof Download PDFInfo
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- CN111205603B CN111205603B CN201811394835.4A CN201811394835A CN111205603B CN 111205603 B CN111205603 B CN 111205603B CN 201811394835 A CN201811394835 A CN 201811394835A CN 111205603 B CN111205603 B CN 111205603B
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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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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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 relates to a biodegradable mulching film and a preparation method thereof, and mainly solves the problems that most agricultural mulching films are not degraded, a small part of mulching films are biodegradable but have poor processability, and the comprehensive properties such as strength, toughness and thickness are difficult to give consideration to in the prior art. The modified polyhydroxyalkanoate material comprises the following components in parts by weight: (1) block type polyhydroxyalkanoate: 10-60 parts; (2) poly (butylene terephthalate) -co-succinate: 30-80 parts of a solvent; (3) a compatilizer: 1-10 parts; (4) chain extender: the technical scheme of 0.1-1 part better solves the problem, and the prepared mulching film meets the requirements of mechanical mulching film laying and comprehensive use, can be completely biodegradable, and can be used in the industrial production of biodegradable mulching films.
Description
Technical Field
The invention relates to a biodegradable mulching film and a preparation method thereof.
Technical Field
The mulching film is used as an important production material in agricultural production, has the effects of improving soil temperature, preventing water evaporation, improving fertilizer efficiency, preventing weeds and the like, and can effectively improve agricultural productivity. The method is widely applied in China, the usage amount of the mulching film in China is increased from 0.6 ten thousand tons in 1982 to 144 ten thousand tons in 2014 according to statistics, the coverage area is over 1800 ten thousand hectares, the application crop types are gradually developed from economic crops to main grain crops such as corn, wheat, rice and the like, and the mulching film application still has a large space for increasing in the future. However, with the popularization and application of the mulching film covering technology, serious residual mulching film pollution problems are caused, and investigation shows that the average residual mulching film amount of the farmland covered with the mulching film for many years is 71.9-259.1kg/hm2The residual mulching film can block the penetration of soil moisture and reduce the soil permeability; and the root system can be prevented from extending, the growth of crops is influenced, the yield of the crops is reduced, and the like, so that the method becomes white pollution in agricultural production.
The development of the biodegradable mulching film is an important technology for solving the problem of white pollution, protecting soil and reducing the workload of farmers, and a great deal of energy is put into the development of the biodegradable mulching film at home and abroad. However, most of the currently reported degradable mulching films are prepared by adding a photosensitizer, starch or calcium carbonate and the like into polyethylene, the mulching films can be disintegrated into small pieces in a certain period, but the polyethylene in the mulching films is not degraded, and the soil can still be seriously polluted. In the aspect of complete biodegradation, at present, enterprises in Jinfa science and technology, Xinfu medicine industry and the like adopt aliphatic copolyester poly (adipic acid) -butylene succinate (PBSA), poly (terephthalic acid) -butylene adipate (PBAT) and the like to carry out a biodegradable mulching film experiment. Mainly made of PBAT and polylactic acid (PLA) as BASF in Germany
The series of biodegradable mulching films are better applied in Germany, Italy and Japan, and enter the Chinese market in 2012, and the biodegradable mulching films of the France Lima glan group comprise PBAT/starch as the main component.
Aliphatic aromatic copolyester (mainly comprising poly (terephthalic acid) -co-butylene succinate and poly (terephthalic acid) -co-butylene adipate) is a rapidly developed high polymer material, is usually obtained by random copolymerization of aliphatic diacid, aromatic diacid and aliphatic diol, and can combine the advantageous properties of the aliphatic polyester and the aromatic polyester to obtain a practical material with excellent strength and toughness. The aromatic polyester segments serve primarily as a dilution cost in addition to providing performance support; the aliphatic polyester segment is generally biodegradable on the basis of providing performance support. The aliphatic aromatic copolyester as a whole will have biodegradability after the aliphatic segment content reaches a certain level, and it is reported in the literature that the biodegradability of the material as a whole is substantially lost after the mole fraction of aliphatic diacid to total diacid is reduced to 38% [ n.honda, i.taniguchi, m.miyamoto, y.kimura, Macromolecular Bioscience,2003,3, 189-. On the other hand, the cost is one of the important factors restricting the large-scale application of the biodegradable polymer material, so in order to reduce the cost of the biodegradable aliphatic aromatic copolyester material, the dosage of the low-price aromatic diacid should be as large as possible on the basis of ensuring the biodegradability. Combining the above two factors, the molar fraction of aliphatic diacid in the biodegradable aliphatic aromatic copolyester material on the market is mostly between 45% and 60% in the total diacid.
Polyhydroxyalkanoate (PHA), a natural polymer biomaterial synthesized by microbial fermentation, has biocompatibility, biodegradability, thermoplastic processability, gas barrier property, etc., and especially, a block-type PHA, can combine processing and mechanical properties of different segments to significantly improve the overall performance, and the Chen group of the Chen Enhance university in Qinghua university makes a lot of works in the related field [ Chen X, Yin J, Ye, J, et al. engineering Halomonas blue TD01 for non-polymer production of poly (3-hydroxybutyric-co-4-hydroxybutyric) [ J ] Bioresource Technology,2017,244:534 ]. However, when used as a biodegradable mulching film material, the PHA material still has the disadvantages of poor thermal stability, easy hydrolysis, relatively narrow processing window, difficult processing and forming, slow crystallization speed, poor toughness, high cost and the like. Patent CN 106589871a uses lignin-modified PHA to make certain progress in mechanical properties and cost, however, it does not clearly describe the thickness of the thin film. The patent CN102229742A adopts plasticizer and the like to modify PHA, and prepares PHA film material by calendaring, however, the thickness of the PHA film material is about 0.05-0.3mm, and the use requirement that the thickness of the mulching film is 0.008-0.02mm in the standard GB13735-92 of biodegradable mulching film can not be met. Patent CN104240660A adopts polyisobutylene, ethylene ethyl acrylate and the like to modify PHA, and successfully prepares a film with the thickness less than 10 microns, the strength is more than 25MPa, and the elongation at break is more than 300%. However, the addition of the non-prodegradant described herein will have a negative effect on the overall degradation performance of the mulch material.
Aiming at the problems, the patent discloses a biodegradable mulching film prepared and processed by an advanced modification technology, which has good processing performance, adjustable thickness of 3-20 microns, tensile breaking elongation of more than 600%, tensile breaking strength of more than 30MPa and elastic modulus of more than 100MPa, meets the requirements of mechanical mulching and comprehensive use, can be completely biodegraded, and has a wide application prospect.
Disclosure of Invention
One of the technical problems to be solved by the invention is that most agricultural mulching films are not degraded in the prior art, and a small part of mulching films are biodegradable but have poor processability and are difficult to give consideration to the comprehensive properties such as strength, toughness, thickness and the like, and the invention provides a modified polyhydroxyalkanoate material which is prepared from the following components in a certain proportion: block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an opening agent and other auxiliary agents. The biodegradable mulching film prepared from the modified polyhydroxyalkanoate material has good processability, the thickness of 3-20 micrometers is adjustable, the tensile breaking elongation is more than 600%, the tensile breaking strength is more than 30MPa, and the elastic modulus is more than 100MPa, so that the requirements of mechanical film laying and comprehensive use are met, the mulching film can be completely biodegradable, and the problems in the prior art are well solved.
The second technical problem to be solved by the present invention is to provide a method for preparing modified polyhydroxyalkanoate material corresponding to the first technical problem.
The invention aims to solve the third technical problem that most agricultural mulching films are not degraded in the prior art, a small part of mulching films are biodegradable but have poor processability, and the comprehensive properties such as strength, toughness and thickness are difficult to be considered simultaneously, and provides a biodegradable mulching film which is prepared from the modified polyhydroxyalkanoate material for solving one of the technical problems.
The fourth technical problem to be solved by the invention is to provide a preparation method of the biodegradable mulching film corresponding to the third technical problem.
In order to solve one of the above technical problems, the invention adopts the technical scheme that: the modified polyhydroxyalkanoate material comprises the following components in parts by weight:
(1) block type polyhydroxyalkanoate: 10-60 parts;
(2) poly (butylene terephthalate) -co-succinate: 30-80 parts of a solvent;
(3) a compatilizer: 1-10 parts;
(4) chain extender: 0.1 to 1 portion.
In the technical scheme, the structure of the block type polyhydroxyalkanoate is shown as the formula (I):
in the formula (I), m, n and l are integers of 3-16, which can be the same or different; r1、R2、R3Is hydrogen atom, alkyl, alkenyl or alkyl with benzene ring, which can be same or different; r1And R2M and n are not the same at the same time; x and x' are 0-200, and are not 0 at the same time. When x is 0, R2And R3N and l are not the same, and when x' is 0, R is1And R3M and l are not the same at the same time. y and z are the statistical average polymerization degrees, and y and z are 10-5000, and can be the same or different.
In the above technical solution, the block type polyhydroxyalkanoate structure is preferably as shown in formula (II):
in the formula (II), x is 1-50, x' is 1-50, y is 50-2000, z is 50-2000, and the weight average molecular weight is 10-80 ten thousand. In the formula (II) — CH2CH2CH2The mass fraction of COO-units in the whole is preferably 5% to 50%, more preferably 8% to 20%.
In the technical scheme, the mole fraction of succinic acid in the polybutylene terephthalate-co-succinate accounts for 40-90% of the total diacid, and is preferably 50-65%.
In the above technical solution, the compatibilizer is at least one of maleic anhydride, acrylates, silane coupling agents and titanate coupling agents, preferably at least one of a copolymer or a graft polymer containing maleic anhydride or acrylate, and more preferably an ethylene-acrylate-maleic anhydride terpolymer or/and ethylene-methyl acrylate-glycidyl methacrylate.
In the above technical solution, the chain extender is a multifunctional compound or polymer capable of reacting with hydroxyl or carbonyl, and is preferably a multifunctional isocyanate or a multifunctional epoxy compound or polymer.
In the above technical solution, the material further preferably includes:
(5) an opening agent: 0.1-10 parts;
(6) other auxiliary agents: 0 to 10 parts.
In the above technical scheme, the opening agent is an auxiliary agent capable of increasing surface roughness or/and reducing surface energy, and includes an inorganic opening agent and an organic opening agent, the inorganic opening agent is at least one of calcium carbonate, talc powder, calcium oxide, titanium dioxide, aluminum oxide, magnesium oxide, boron nitride, silicon oxide, carbon black, mica and chalk powder, and the organic opening agent is at least one of oleamide and erucamide.
In the technical scheme, the other auxiliary agent is at least one of an anti-hydrolysis agent, an ultraviolet absorbent, an antioxidant, a light stabilizer and the like.
In order to solve the second technical problem, the invention adopts the technical scheme that: a method for preparing a modified polyhydroxyalkanoate material according to any one of the above technical solutions:
adding required amount of block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an opening agent and optional other auxiliary agents into a double-screw extruder, and mixing, melting, reacting and extruding to obtain the modified polyhydroxyalkanoate material.
In the above technical scheme, the rotation speed of the twin-screw extruder is preferably 80 to 400 rpm; the extrusion temperature is preferably from 130 ℃ to 190 ℃.
In order to solve the third technical problem, the invention adopts the technical scheme that: a biodegradable mulching film comprises the modified polyhydroxyalkanoate material in the technical scheme for solving the technical problem.
In the technical scheme, the thickness of the biodegradable mulching film is preferably 3-20 micrometers, more preferably 3-10 micrometers, and still more preferably 3-6 micrometers; the tensile elongation at break is preferably > 600%; the tensile break strength is preferably >30 MPa; the modulus of elasticity is preferably >100 MPa.
In order to solve the fourth technical problem, the invention adopts the technical scheme that: the preparation method of the biodegradable mulching film in any one of the third technical scheme for solving the technical problems comprises the following steps:
adding required amount of block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an opening agent and optional other auxiliary agents into a double-screw extruder, mixing, melting, reacting, extruding, cooling and granulating to obtain modified polyhydroxyalkanoate material granules, adding the modified polyhydroxyalkanoate material granules into a single-screw extrusion film blowing machine, and melting, extruding, drafting, cooling and shaping to obtain the biodegradable mulching film;
or: adding required amount of block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an opening agent and optional other auxiliary agents into a double-screw extruder, mixing, melting, reacting, pressurizing by a melt pump, extruding to a film blowing die, drafting, cooling and sizing to obtain the biodegradable mulching film.
In the above technical scheme, the rotation speed of the twin-screw extruder is preferably 80 to 400 rpm; the extrusion temperature is preferably from 130 ℃ to 190 ℃.
In the above technical solution, the rotation speed of the single screw extruder is preferably 30 to 200 rpm; the extrusion temperature is preferably from 130 ℃ to 190 ℃.
In the above technical solution, the ratio (blow-up ratio) of the diameter of the shaped bubble to the diameter of the die is preferably 2: 1-6: 1.
in the technical scheme, the thickness of the biodegradable mulching film is preferably 3-20 micrometers, more preferably 3-10 micrometers, and still more preferably 3-6 micrometers.
By adopting the technical scheme of the invention, the obtained modified polyhydroxyalkanoate material better solves the problems that the existing biodegradable mulching film is poor in processability and difficult to give consideration to the comprehensive properties such as strength, toughness and thickness, and the like, and the biodegradable mulching film with excellent comprehensive properties is prepared, wherein the thickness of the biodegradable mulching film is as follows: 3-20 microns, tensile elongation at break: > 600%, tensile break strength: >30MPa, modulus of elasticity: 100MPa, meets the requirements of mechanical film laying and comprehensive use, has higher popularization and application values, and obtains better technical effects. The invention carries out performance measurement according to the following method:
film thickness: the average value is obtained by uniformly measuring 10 points by using the GB/T6672-2001 standard test.
Mechanical properties: the test was carried out in accordance with ISO 527-3 using a model 3344 film tester from INSTRON, the processing software being Bluehill version 2.31. The film was cut into Type 5 according to ISO 527-3, and placed in a Bluepard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hengchan scientific instruments Co., Ltd. for 24 hours. During testing, the initial clamp spacing was 75mm, the test pull rate was 500mm/min, and each sample was tested 5 times, and the average value was taken.
Detailed Description
The present invention is specifically described by the following examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
[ example 1 ]
The block type polyhydroxyalkanoate used in the invention is prepared by biological fermentation, the specific molecular structure is that 3-hydroxybutyric acid and 4-hydroxybutyric acid are randomly copolymerized and then are block copolymerized with 3-hydroxybutyric acid (bPHA), the weight average molecular weight is about 50 ten thousand, wherein the mass fraction of the 4-hydroxybutyric acid is about 18%, the mass fraction of the block copolymerized 3-hydroxybutyric acid is about 50%, and the mass fraction of the random copolymerized 3-hydroxybutyric acid is about 32%.
The 1, 4-succinic acid, the terephthalic acid, the 1, 4-butanediol, the tetraisopropyl titanate and the pentaerythritol which are used in the invention are CP grade products of national chemical and chemical test companies. In a reaction kettle for completely removing water and oxygen, 1, 4-succinic acid and terephthalic acid respectively account for 50 percent and 50 percent of the molar ratio of the total diacid feeding amount, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, and cut into cylindrical particles having a length of about 3mm by a pelletizer for cooling in a room temperature water bath. The PBST particles were dried at 60 ℃ for 4hr, cooled and packaged (named PBST-S50).
Firstly drying assistants such as bPHA, PBST-S50, a compatibilizer, a chain extender, an opening agent and the like in a vacuum oven at 60 ℃ for 4 hours, and removing water. Then, according to the mass parts, 10 parts of bPHA, 5074.5 parts of PBST-S, 10 parts of a compatibilizer, 0.5 part of a chain extender, 4.5 parts of an inorganic opening agent and 0.5 part of an organic opening agent are fully mixed and then added into a double screw to be extruded and granulated, so as to obtain the biodegradable mulching film granules. The twin screw was a PolyLab HAAKE Rheomex OS PTW16 co-rotating twin screw extruder (screw diameter 16mm, length-to-diameter ratio L/D40) from ThermoFisher technologies, USA. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 150 ℃,160 ℃,170 ℃,170 ℃,170 ℃,170 ℃,170 ℃,170 ℃,170 ℃, and 160 ℃, with the screw speed set at 200 rpm. When the engine runs stably, the torque is 40-60% of the maximum value. The extruder was equipped with a circular die having a diameter of 3mm, and the sample strip was extruded from the die, air-cooled, and cut into cylindrical pellets having a set diameter of about 3mm by a cutter. The obtained particles were dried in a vacuum oven at 60 ℃ for 4 hours, and then packaged for use.
[ example 2 ]
The implementation mode is the same as that of the example 1, but the mass parts of the components are changed into 20 parts of bPHA, 5064.5 parts of PBST-S, 10 parts of a compatibilizer, 0.5 part of a chain extender, 4.5 parts of an inorganic opening agent and 0.5 part of an organic opening agent.
[ example 3 ]
The embodiment is the same as the example 1, but the parts by mass of the components are changed into bPHA 30 parts, PBST-S5064.5 parts, compatibilizer 10 parts, chain extender 0.5 part, inorganic opening agent 4.5 parts and organic opening agent 0.5 part.
[ example 4 ]
Three biodegradable mulch film granules prepared in examples 1 to 3 were extruded and blown into films by a single screw extruder (PolyLab HAAKE Rheomex 252OS) equipped with a film blowing accessory, the single screw having three heating zones and four heating zones including a die head, the temperatures were set at 150 ℃,160 ℃,160 ℃ and 160 ℃, respectively, and the blowing ratio was controlled to be 4: 1. the film thickness was controlled by controlling the stretching speed and the screw rotation speed. Example 1 can produce a film of 3 microns with the thinnest pellet, example 2 can produce a film of 4 microns with the thinnest pellet, and example 3 can produce a film of 5 microns with the thinnest pellet.
[ example 5 ]
The three films obtained in example 4 were subjected to mechanical property tests in the thinnest state in the same manner as described above, and the drawing direction (MD) and the vertical drawing direction (CD) were measured. The results are shown in Table 1.
TABLE 1 mechanical Properties of biodegradable films
| Sample(s) | Thickness/mum | Tensile strength/MPa | Elongation at break/% | Modulus of elasticity/MPa |
| Example 1 MD | 3 | 37 | 415 | 140 |
| Example 1 CD | 3 | 35 | 765 | 128 |
| Example 2 MD | 4 | 35 | 375 | 127 |
| Example 2 CD | 4 | 34 | 704 | 120 |
| Example 3 MD | 5 | 34 | 343 | 121 |
| Example 3 CD | 5 | 32 | 669 | 112 |
Claims (10)
1. The modified polyhydroxyalkanoate material comprises the following components in parts by weight:
(1) block type polyhydroxyalkanoate: 10-60 parts;
(2) poly (butylene terephthalate) -co-succinate: 30-80 parts of a solvent;
(3) a compatilizer: 1-10 parts;
(4) chain extender: 0.1-1 part;
wherein, the structure of the block type polyhydroxyalkanoate is shown as the formula (II):
in the formula (II), x = 1-50, x' = 1-50, y = 50-2000, z = 50-2000, and the weight average molecular weight is 10-80 ten thousand; in the formula (II) — CH2CH2CH2The mass fraction of COO-chain links in the whole is 5-50%;
the mol fraction of succinic acid in the poly (terephthalic acid) -co-butylene succinate is 40-90 percent of the total diacid;
the compatilizer is at least one of copolymers containing maleic anhydride or acrylic ester.
2. The modified polyhydroxyalkanoate material of claim 1, wherein the polybutylene terephthalate-co-succinate comprises 50% to 65% by mole of the total diacid.
3. The modified polyhydroxyalkanoate material of claim 1, wherein the compatibilizer is an ethylene-acrylate-maleic anhydride terpolymer or/and an ethylene-methyl acrylate-glycidyl methacrylate terpolymer.
4. The modified polyhydroxyalkanoate material of claim 1, wherein the chain extender is a multifunctional isocyanate or a multifunctional epoxy compound or a polymer.
5. The modified polyhydroxyalkanoate material of claim 1, characterized in that the material further comprises:
(5) an opening agent: 0.1-10 parts;
(6) other auxiliary agents: 0-10 parts;
the opening agent is an auxiliary agent capable of increasing the surface roughness or/and reducing the surface energy; the other auxiliary agent is at least one of hydrolytic resistance agent, antioxidant and light stabilizer.
6. The modified polyhydroxyalkanoate material of claim 5, wherein the opening agent comprises an inorganic opening agent and an organic opening agent.
7. The modified polyhydroxyalkanoate material of claim 6, wherein the inorganic opening agent is at least one of calcium carbonate, talc, calcium oxide, titanium dioxide, alumina, magnesium oxide, boron nitride, silica, mica, chalk powder, and the organic opening agent is at least one of oleamide, erucamide.
8. A method for preparing the modified polyhydroxyalkanoate material of any one of claims 1 to 7, comprising the steps of:
adding required amount of block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an optional opening agent and optional other auxiliary agents into a double-screw extruder, and mixing, melting, reacting and extruding to obtain the modified polyhydroxyalkanoate material.
9. A biodegradable mulch film comprising the modified polyhydroxyalkanoate material of any one of claims 1 to 7.
10. A method for preparing the biodegradable mulch film according to claim 9, comprising the steps of:
adding required amount of block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an optional opening agent and optional other auxiliary agents into a double-screw extruder, mixing, melting, reacting, extruding, cooling and granulating to obtain modified polyhydroxyalkanoate material granules, adding the modified polyhydroxyalkanoate material granules into a single-screw extrusion film blowing machine, and melting, extruding, drafting, cooling and shaping to obtain the biodegradable mulching film;
or: adding required amount of block type polyhydroxyalkanoate, poly (terephthalic acid) -co-butylene succinate, a compatilizer, a chain extender, an optional opening agent and optional other auxiliary agents into a double-screw extruder, mixing, melting, reacting, pressurizing by a melt pump, extruding to a film blowing die, drafting, cooling and sizing to obtain the biodegradable mulching film.
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| CN114474641A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Film production device and biodegradable mulching film produced by same |
| CN112759901A (en) * | 2020-12-29 | 2021-05-07 | 四川坤源杰环保科技有限公司 | Micro-crystallization toughening modified PBS or PBAT biodegradable composite material |
| WO2024029492A1 (en) * | 2022-08-01 | 2024-02-08 | Dic株式会社 | Copolyester comprising 3-hydroxybutyric acid and method for producing same |
| CN115926400A (en) * | 2023-01-03 | 2023-04-07 | 深圳市鼎力盛科技有限公司 | New material environment-friendly calabash film, preparation method and application thereof |
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