CN114369345B - High-barrier full-biodegradable mulching film with fertilizer effect and preparation method thereof - Google Patents
High-barrier full-biodegradable mulching film with fertilizer effect and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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- C05G5/00—Fertilisers characterised by their form
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- 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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Abstract
The application provides a high-barrier full-biodegradable mulch film with a fertilizer effect and a preparation method thereof. The material is prepared from the following raw materials in percentage by weight: PBAT resin: 68-84%, and high crystallinity polylactic acid: 10-20% of a blocking agent: 0.1-10% of chain extender: 0.1-0.5%, anti-UV agent: 0.1-1.0%, light stabilizer: 0.5-1.0%, antioxidant: 0.3-0.5%, and an anti-hydrolysis agent: 0.1-0.5%, and an opening agent: 0.5-2.0%. The interfacial compatibility of the barrier agent and the PBAT resin is greatly improved when melt blending is carried out, the barrier agent is promoted to be well dispersed in the PBAT resin, and the multi-element organic phosphoric acid and urea are deposited on the structure of the barrier agent in a chemical bonding mode, so that the obtained full-biodegradable mulch film has the effect of continuously guaranteeing the growth of crops as a fertilizer in the degradation process, and the mulch film laying strength and the comprehensive performances in the aspects of heat preservation, water preservation, fertilizer preservation, soil moisture preservation and the like are effectively improved.
Description
Technical Field
The application belongs to the technical field of agricultural mulching films, and particularly relates to a high-barrier full-biodegradable mulching film with a fertilizer effect and a preparation method thereof.
Background
The agricultural mulching film can effectively control the temperature and humidity of soil, reduce the loss of water and nutrients, prevent weed growth, create a favorable ecological environment for crop growth, and is one of the effective ways for increasing the yield of food and economic crops in the world. China is a large agricultural country, the coverage area of the mulch film in China is up to 2 hundred million mu at present, the annual consumption is about 100 ten thousand tons, and the coverage area and the consumption are the first in the world. However, the plastic film mulching technology brings economic benefits to the agriculture and also seriously pollutes the land. At present, chemical fibers are widely used as raw materials for agricultural films, the main components of the agricultural films are polyethylene and polyvinyl chloride, most of traditional plastics are stable in performance, are not easily degraded rapidly under the action of various environmental factors in nature, can be remained in fields for decades without degradation, and can be accumulated on soil cultivation layers year by year after year due to broken films used in successive years, so that soil hardening, permeability deterioration and root growth resistance are caused, and the yield of succeeding products is reduced.
At present, the problem of residual film pollution is mainly solved in two main directions of recycling and popularization and degradation of the mulching film. The recycling has the defects of low residual film recovery rate, serious secondary processing pollution, high manual picking-up cost and the like, and the full-biodegradable plastic can be eroded and digested into carbon dioxide, water, other biomass and inorganic matters by microorganisms in a short time, so that the full-biodegradable plastic is an environment low-load material. Therefore, in the long term development, popularization and use of the full-biodegradable mulch film are considered to be the most fundamental and effective way to solve the problem of residual film pollution.
In the research and popularization process, a plurality of problems are encountered, in particular, the total biodegradable material has high water vapor transmission capacity, so that the soil moisture conservation performance of the mulching film is poor, and the degradation process is not stable and controllable. In view of the characteristics of the fully biodegradable mulch film material, several problems still need to be overcome before large-scale application: firstly, operability, the tensile strength of the mulching film needs to meet the requirement of film covering operation, and especially in a large-scale mechanized operation farm area, the mechanical property of the mulching film needs to meet the requirement of mechanized film covering operation; secondly, the functional requirements of heating, preserving moisture, inhibiting grass and the like, which are beneficial to the growth of crops, are met after the film is coated; and thirdly, the controllability, namely that the mulching film is broken and degraded only after the basic functions of the mulching film are completed, and especially the mulching film cannot be broken and degraded prematurely.
The application patent of CN109054309A discloses a preparation method of PLA high barrier mulching film, which is prepared by taking polylactic acid as a matrix, selecting a small amount of polyglycolic acid with specific molecular weight and polybutylene terephthalate adipate, and blowing the film after melt extrusion. The base material used for the mulching film is polylactic acid, is not suitable for molding and processing of polyester films, and does not have high barrier property. The application patent of CN101815748A discloses a biodegradable biaxially oriented composite film, which is based on polylactic acid-based polymer and aromatic polyester-based resin, and realizes the improvement of the barrier performance of the fully biodegradable mulching film by a melt extrusion-biaxially oriented method of the polylactic acid-based polymer and the aromatic polyester-based resin, but the barrier system in the patent is simply mixed with a plurality of inert inorganic particles, and has the problems of difficult dispersion of a barrier agent in matrix resin, large addition amount, barrier efficiency and the like. The application patent of CN108377821A discloses a biodegradable barrier mulch film, which is prepared by in-situ melt polycondensation of barrier filler, and then entering matrix resin, and in-situ reaction of the resin in the processing process, so as to balance the weather resistance and biodegradability of the mulch film and realize controllable degradation of the mulch film. However, the mulching film prepared by the patent is of a three-layer composite structure, has thicker film thickness, is difficult to produce, has difficult quality control and is difficult to realize industrialization.
Disclosure of Invention
The application aims to solve the problems that the full-biodegradable mulching film in the prior art has low film laying strength, and is difficult to meet the use requirements in the aspects of heat preservation, water preservation, fertilizer preservation, soil moisture preservation and the like, and provides a high-barrier full-biodegradable mulching film with a fertilizer effect and a preparation method thereof. The full-biodegradable mulch film prepared by the application has the advantages of low addition amount of the barrier agent, high barrier property and the like, and can be used as a fertilizer to continuously ensure the growth of crops in the mulch film degradation process.
In order to achieve the aim of the application, the application is realized by the following technical scheme:
the high-barrier full-biodegradable mulching film with the fertilizer effect is prepared from the following raw materials in percentage by weight:
PBAT resin: 68 to 84 percent
High crystallinity polylactic acid: 10 to 20 percent
Blocking agent: 0.1 to 10 percent
Chain extender: 0.1 to 0.5 percent
UV-resistant agent: 0.1 to 1.0 percent
Light stabilizers: 0.5 to 1.0 percent
An antioxidant: 0.3 to 0.5 percent
Hydrolysis inhibitor: 0.1 to 0.5 percent
And (3) an opening agent: 0.5 to 2.0 percent.
In the application, the blocking agent is P-MgAl-NO with a reactive NH-CO bond and a fertilizer effect 3 -LDHs blocking agents;
the preparation method of the barrier agent comprises the following steps:
(1) 1 to 30 parts of polybasic organic phosphoric acid is dissolved in 20 to 80 parts of deionized water at the temperature of 50 to 70 ℃, and then 10 to 60 parts of nitric acid type magnesium aluminum hydrotalcite MgAl-NO is added into the solution 3 LDHs, stirring and heat preservation for 1-3 days, then suction filtering and drying the obtained product, introducing the multi-element organic phosphoric acid into MgAl-NO through surface modification 3 In LDHs, surface modified P-MgAl-NO is obtained 3 -LDHs；
(2) 5 to 40 parts of P-MgAl-NO after surface modification 3 Adding LDHs, 30-80 parts of deionized water and 10-60 parts of urea into a reactor, starting stirring, heating the reactor to 60-100 ℃ and preserving heat for 0.5-2.5 h;
(3) After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 3 to 12 hours, and urea is deposited to P-MgAl-NO in a chemical bonding mode after being filtered and dried 3 The structure of LDHs can obtain P-MgAl-NO with reactive NH-CO bond and fertilizer effect 3 -LDHs blocking agents;
the barrier agent prepared by the application adopts the multi-component organic phosphoric acid to carry out surface modification on the traditional LDHs, replaces a large amount of-OH on the surface of the LDHs, successfully introduces the-POOH group with reactivity, further deposits urea on the structure of the LDHs in a chemical bonding mode, and finally obtains the fertilizer-effect beltP-MgAl-NO capable of reacting NH-CO bond 3 LDHs. On one hand, the barrier agent and the PBAT matrix effectively improve the interface compatibility of the barrier agent and the PBAT matrix during melt blending, and overcome the defects of large addition amount of the barrier agent and poor dispersibility in the PBAT matrix in a similar method; on the other hand, the multi-element organic phosphoric acid and urea are deposited on the structure of the blocking agent in a chemical bonding mode, so that N, P two chemical fertilizer elements are successfully introduced, and the mulching film has the effect of continuously guaranteeing the growth of crops as a fertilizer in the degradation process;
in the preparation method of the blocking agent, the polybasic organic phosphoric acid is one or more of amino trimethyl phosphate, hydroxy ethylidene diphosphate, diethylenetriamine pentamethylene phosphate and ethylenediamine tetramethylene phosphate.
In the application, the molecular weight of the PBAT resin is 5-20 ten thousand, and the melt index is 2-10 g/10min (190 ℃,2.16 kg).
In the application, the high crystallinity polylactic acid has the molecular weight of 5-10 ten thousand, the density of 1.2-1.35 g/cm3, the melt index of 3-8 g/10min (190 ℃,2.16 kg), the melting point of 170-180 ℃, the tensile strength of 42-55 MPa, the elongation at break of 6-15% and the impact strength of 5-12 KJ/m 2 。
In the application, the chain extender is one or more of epoxy chain extender, hexamethylene diisocyanate and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.
In the present application, the anti-UV agent is one or more of UV234, UV320, UV327 and UV-P.
In the present application, the light stabilizer is one or more of the light stabilizer 622, the light stabilizer 770, the light stabilizer 783 and the light stabilizer 944.
In the application, the antioxidant is one or more of 1076, 1010, 618, DLTP and DSTP.
In the application, the hydrolysis inhibitor is one or more of carbodiimide monomer, N' -bis (2, 6-diisopropylphenyl) carbodiimide, toluene-2, 4-diisocyanate and diphenylmethane diisocyanate.
In the application, the opening agent is one or more of erucamide, oleamide, talcum powder, diatomite and ethylene bis-stearamide.
The preparation method of the high-barrier full-biodegradable mulching film with the fertilizer effect comprises the following steps:
(1) Preferably, the PBAT resin and the high crystallinity polylactic acid are dried for 2 to 6 hours at the temperature of 60 to 90 ℃ before being used;
(2) Adding PBAT resin, high crystallinity polylactic acid, a blocking agent, a chain extender, an anti-UV agent, a light stabilizer, an antioxidant, an anti-hydrolysis agent and an opening agent into a high-speed mixer, fully mixing for 5-20 min, adding the uniformly mixed materials into a double-screw extruder with the length-diameter ratio of less than or equal to 35 and less than or equal to 50 through a feeder, extruding and granulating in the range of 60-180 ℃, and drying the prepared granules for 1-3 hours at the temperature of 60-100 ℃;
(3) Adding the dried granules into a film extrusion blow molding machine with the length-diameter ratio of less than or equal to 25 and less than or equal to 40, and controlling the blowing ratio to be 1-3 within the range of 150-190 ℃:1, extruding and blow molding to obtain the high-barrier full-biodegradable mulch film with fertilizer effect, wherein the thickness of the mulch film is preferably 0.006-0.015 mm.
The application has the beneficial effects that: the application selects and adds a certain content of P-MgAl-NO with a fertilizer function and a reactive NH-CO bond 3 The LDHs blocking agent improves the interfacial compatibility of the LDHs blocking agent and the matrix resin when the LDHs blocking agent is melt blended with the matrix resin, ensures good dispersion of the blocking agent in the matrix, and ensures that the blocking agent can better exert the blocking effect; meanwhile, the obtained full-biodegradable mulching film has the function of continuously guaranteeing the growth of crops as a fertilizer in the degradation process. Finally, P-MgAl-NO 3 The addition amount of the LDHs is as low as 3 percent, the transverse tensile strength and the longitudinal tensile strength of the fully biodegradable mulch film can still reach 48.2MPa and 50.4MPa respectively, the elongation at break reaches 621.4 percent and 645.5 percent, and the water vapor transmission amount reaches 92.1 g/(m) 2 24 h), has the characteristics of excellent mechanical strength, high barrier, fertilizer conservation and soil moisture conservation. The mechanical property of the high-barrier full-biodegradable mulch film with fertilizer effect provided by the application is more than twice that of the traditional PE mulch film, and the barrier is highThe barrier property is also obviously superior to other full-biodegradable mulch films, the mulch film has simple manufacturing process and easy industrialized production, and has very important significance for solving the white pollution of farmlands in China and improving the agricultural cultivation efficiency.
Detailed Description
The raw material information used in the following examples and comparative examples is:
PABT is 801T, purchased from Xinjiang blue mountain Tunche; the high crystallinity polylactic acid is L175, purchased from dadaceae pyn; P-MgAl-NO with reactive NH-CO bond 3 The LDHs blocking agent is self-made; the chain extender was ADR4468, available from BASF, germany; the anti-UV agent is UV234, purchased from angeli An Long; the light stabilizer is light stabilizer 944, available from Tianjin An Long; antioxidants 618 and 1076, purchased from angelicas An Long; the hydrolysis resistance agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, available from Nicotine New chemical; the opener is erucamide, purchased from Shanghai He Dagae chemical; nitric acid type magnesium aluminum hydrotalcite (MgAl-NO) 3 LDHs) were purchased from shandong molal chemical industry.
The conventional mechanical properties and the barrier properties of the fully biodegradable mulch were tested according to the following criteria, the results are shown in Table 1:
tensile strength: testing conditions of the films and sheets in the third part were determined according to GB/T1040.3-2006 plastic tensile properties, with a tensile rate of 200mm/min;
water Vapor Transmission (WVT): the test conditions were as defined in GB/T1037: the temperature is 38+/-0.6 ℃ and the relative humidity is 90+/-2 percent.
The application will be further elucidated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Further, it is understood that various changes and modifications of the present application may be made by those skilled in the art after reading the description of the present application, and such equivalents are intended to fall within the scope of the application as defined in the claims.
The parts described in the examples are all parts by mass.
Example 1
Blocking agent: P-MgAl-NO with reactive NH-CO bond 3 Preparation of LDHsThe preparation method comprises the following steps: 5 parts of hydroxyethylidene diphosphate are dissolved in 30 parts of deionized water at 60℃and 15 parts of magnesium aluminum hydrotalcite MgAl-NO of the nitric acid type are added thereto 3 LDHs, stirring and heat preservation for 2 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs; then 5 parts of the surface-modified P-MgAl-NO 3 LDHs, 30 parts of deionized water and 10 parts of urea were added to the reactor and stirring was started and the reactor was warmed to 80 ℃ and incubated for 0.5h. After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 6 hours, and the P-MgAl-NO with the reactive NH-CO bond and the fertilizer effect is obtained after suction filtration and drying 3 -LDHs blocking agents.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 84%
L175：12％
Blocking agent: 1%
ADR 4468：0.1％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.4%
Erucamide: 1%
(1) Drying the PBAT resin and the high-crystallinity polylactic acid for 2 hours at 80 ℃ before use; (2) Adding the dried PBAT resin, the high crystallinity polylactic acid, the blocking agent, the chain extender, the UV resistant agent, the light stabilizer, the antioxidant, the hydrolysis resistant agent and the opening agent into a high-speed mixer, fully mixing for 10min, adding the uniformly mixed materials into a double-screw extruder with the length-diameter ratio of=35 through a feeder, extruding and granulating in the range of 60-180 ℃, and drying the prepared granules for 2 hours at the temperature of 80 ℃; (3) Adding the dried granules into a film extrusion blow molding machine with the length-diameter ratio of=25, and controlling the blowing ratio to be 3 within the range of 150-190 ℃:1, preparing the high-barrier full-biodegradable mulch film with fertilizer effect through an extrusion blow molding process, wherein the thickness of the mulch film is 0.01mm.
Example 2
Blocking agent: P-MgAl-NO with reactive NH-CO bond 3 The preparation method of the LDHs comprises the following steps: 12 parts of hydroxyethylidene diphosphate are dissolved in 35 parts of deionized water at 55℃and 20 parts of magnesium aluminum hydrotalcite MgAl-NO of the nitric acid type are added thereto 3 LDHs, stirring and heat preservation for 1.5 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs; then 14 parts of surface-modified P-MgAl-NO 3 LDHs, 40 parts of deionized water and 24 parts of urea were added to the reactor and stirring was started and the reactor was warmed to 70 ℃ and incubated for 1h. After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 5 hours, and the P-MgAl-NO with the reactive NH-CO bond and the fertilizer effect is obtained after suction filtration and drying 3 -LDHs blocking agents.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 80 percent of
L175：14％
Blocking agent: 3%
ADR 4468：0.2％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.3%
Erucamide: 1%
The preparation method is the same as in example 1.
Example 3
Blocking agent: P-MgAl-NO with reactive NH-CO bond 3 The preparation method of the LDHs comprises the following steps: at 60℃18 parts of hydroxyethylidene diphosphate were dissolved in 55 parts of deionized water, followed by the addition thereto of 32 parts of magnesium aluminium hydrotalcite MgAl-NO of the nitric acid type 3 LDHs, stirring and heat preservation for 2 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs; then 22 parts of the surface are modifiedPost P-MgAl-NO 3 LDHs, 55 parts deionized water and 36 parts urea were added to the reactor and stirring was turned on and the reactor was warmed to 80 ℃ and incubated for 1.5h. After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 7 hours, and the P-MgAl-NO with the reactive NH-CO bond and the fertilizer effect is obtained after suction filtration and drying 3 -LDHs blocking agents.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 76%
L175：16％
Blocking agent: 5%
ADR 4468：0.4％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.5%
Erucamide: 0.6%
The preparation method is the same as in example 1.
Example 4
Blocking agent: P-MgAl-NO with reactive NH-CO bond 3 The preparation method of the LDHs comprises the following steps: 25 parts of hydroxyethylidene diphosphate are dissolved in 70 parts of deionized water at 65℃and 45 parts of magnesium aluminum hydrotalcite MgAl-NO of the nitric acid type are added thereto 3 LDHs, stirring and heat preservation for 2.5 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs; then 30 parts of the surface-modified P-MgAl-NO 3 LDHs, 68 parts deionized water and 48 parts urea were added to the reactor and stirring was turned on and the reactor was warmed to 90 ℃ and incubated for 2h. After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 10 hours, and the P-MgAl-NO with the reactive NH-CO bond and the fertilizer effect is obtained after suction filtration and drying 3 -LDHs blocking agents.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 72 percent of
L175：18％
Blocking agent: 7%
ADR 4468：0.4％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.3%
Erucamide: 0.8%
The preparation method is the same as in example 1.
Example 5
Blocking agent: P-MgAl-NO with reactive NH-CO bond 3 The preparation method of the LDHs comprises the following steps: 25 parts of hydroxyethylidene diphosphate are dissolved in 80 parts of deionized water at 65℃and 60 parts of magnesium aluminum hydrotalcite MgAl-NO of the nitric acid type are added thereto 3 LDHs, stirring and heat preservation for 2 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs; then 30 parts of the surface-modified P-MgAl-NO 3 LDHs, 80 parts deionized water and 60 parts urea were added to the reactor and stirring was started and the reactor was warmed to 70 ℃ and incubated for 2.5h. After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 5 hours, and the P-MgAl-NO with the reactive NH-CO bond and the fertilizer effect is obtained after suction filtration and drying 3 -LDHs blocking agents.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 68%
L175：20％
Blocking agent: 9%
ADR 4468：0.5％
UV234：0.5％
Light stabilizer 944:0.5%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.2%
Erucamide: 0.8%
The preparation method is the same as in example 1.
Comparative example 1
The blocking agent is outsourced nitric acid type magnesium aluminum hydrotalcite (MgAl-NO) 3 -LDHs)。
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 80 percent of
L175：14％
Blocking agent: 3%
ADR 4468：0.2％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.3%
Erucamide: 1%
The preparation method is the same as in example 1.
Comparative example 2
Blocking agent: surface modified P-MgAl-NO 3 The preparation method of the LDHs comprises the following steps: 12 parts of hydroxyethylidene diphosphate are dissolved in 35 parts of deionized water at 55℃and 20 parts of magnesium aluminum hydrotalcite MgAl-NO of the nitric acid type are added thereto 3 LDHs, stirring and heat preservation for 1.5 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs。
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 80 percent of
L175：14％
Blocking agent: 3%
ADR 4468：0.2％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.3%
Erucamide: 1%
The preparation method is the same as in example 1.
Comparative example 3
Blocking agent: P-MgAl-NO with reactive NH-CO bond 3 The preparation method of the LDHs comprises the following steps: 12 parts of hydroxyethylidene diphosphate are dissolved in 35 parts of deionized water at 55℃and 20 parts of magnesium aluminum hydrotalcite MgAl-NO of the nitric acid type are added thereto 3 LDHs, stirring and heat preservation for 1.5 days, and then suction filtering and drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs; then 14 parts of surface-modified P-MgAl-NO 3 LDHs, 40 parts of deionized water and 24 parts of p-phenylenediamine were added to the reactor and stirring was turned on, and the reactor was warmed to 70 ℃ and incubated for 1h. After the reaction is finished, the obtained product is stood at room temperature, naturally cooled, crystallized and separated out for 5 hours, and the P-MgAl-NO with the reactive NH-CO bond and the fertilizer effect is obtained after suction filtration and drying 3 -LDHs blocking agents.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT pellets: 80 percent of
L175：14％
Blocking agent: 3%
ADR 4468：0.2％
UV234：0.4％
Light stabilizer 944:0.6%
1076 and 618 (1:2): 0.5%
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.3%
Erucamide: 1%
The preparation method is the same as in example 1.
As can be seen from the test results of examples 1 to 5 and comparative examples 1 to 3 in Table 1, the present application was used to prepare P-MgAl-NO having a reactive NH-CO bond 3 The fully biodegradable mulch prepared by the LDHs blocking agent solves the problems that the compatibility of the traditional blocking agent and the matrix PBAT resin is poor, and the large agent is largeThe product performance is reduced when the amount is added, the problems of difficult satisfaction of use requirements in the aspects of heat preservation, water preservation, fertilizer preservation, soil moisture preservation and the like are solved, the film laying strength of the material is improved, the water vapor transmission amount is reduced, the barrier property of the film is improved, and the mulching film can be used as a fertilizer to continuously ensure the growth of crops in the degradation process.
It should be understood that the above examples of the present application are provided for clarity of illustration only and are not intended to limit the embodiments of the present application. Various other changes and modifications may be made by one skilled in the art in light of the above teachings, and it is not necessary or desirable to exemplify all embodiments herein. Any modification, equivalent replacement or variation which comes within the spirit and principle of the present application shall fall within the protection scope of the claims of the present application.
Claims (10)
1. A high-barrier full-biodegradable mulch film with fertilizer effect is characterized in that: the material is prepared from the following raw materials in percentage by weight:
PBAT resin: 68 to 84 percent
High crystallinity polylactic acid: 10 to 20 percent
Blocking agent: 0.1 to 10 percent; the blocking agent is P-MgAl-NO with a reactive NH-CO bond and fertilizer effect 3 -LDHs blocking agents;
chain extender: 0.1 to 0.5 percent
UV-resistant agent: 0.1 to 1.0 percent
Light stabilizers: 0.5 to 1.0 percent
An antioxidant: 0.3 to 0.5 percent
Hydrolysis inhibitor: 0.1 to 0.5 percent
And (3) an opening agent: 0.5 to 2.0 percent.
2. The mulch film according to claim 1, wherein: the preparation method of the barrier agent comprises the following steps:
(1) At 50-70 ℃, the polynary organic phosphoric acid is dissolved in deionized water, and the nitric acid type magnesium aluminum hydrotalcite MgAl-NO is added 3 -LDHs，Stirring and preserving heat, and then drying the obtained product to obtain the surface modified P-MgAl-NO 3 -LDHs；
(2) Surface-modified P-MgAl-NO 3 Adding LDHs, deionized water and urea into a reactor, heating to 60-100 ℃ and preserving heat; after the reaction is finished, crystallizing and separating out the obtained product, and drying to obtain the P-MgAl-NO with the fertilizer effect and the reactable NH-CO bond 3 -LDHs blocking agents.
3. The mulch film according to claim 2, wherein: the polybasic organic phosphoric acid is one or more of amino trimethyl phosphate, hydroxy ethylene diphosphate, diethylene triamine pentamethylene phosphate and ethylene diamine tetramethylene phosphate.
4. A mulch film according to claim 2 or claim 3 wherein: in the step (1), the dosages of the components are as follows: 1 to 30 parts of polybasic organic phosphoric acid, 20 to 80 parts of deionized water, 10 to 60 parts of nitric acid type magnesium aluminum hydrotalcite MgAl-NO 3 -LDHs; preserving heat for 1-3 days;
in the step (2), the dosages of the components are as follows: 5-40 parts of surface-modified P-MgAl-NO 3 -LDHs, 30-80 parts deionized water and 10-60 parts urea; preserving heat for 0.5-2.5 h.
5. A mulch film according to any one of claims 1-3 wherein: the molecular weight of the PBAT resin is 5-20 ten thousand, and the melt index under the condition of 190 ℃/2.16kg is 2-10 g/10min; and/or:
the molecular weight of the high crystallinity polylactic acid is 5-10 ten thousand, and the density is 1.2-1.35 g/cm 3 The melt index under the condition of 190 ℃/2.16kg is 3 to 8g/10min, the melting point is 170 to 180 ℃, the tensile strength is 42 to 55MPa, the elongation at break is 6 to 15 percent, and the impact strength is 5 to 12KJ/m 2 。
6. A mulch film according to any one of claims 1-3 wherein: the chain extender is one or more of epoxy chain extender, hexamethylene diisocyanate and ethylene-methyl acrylate-glycidyl methacrylate terpolymer; and/or:
the anti-UV agent is one or more of UV234, UV320, UV327 and UV-P; and/or:
the light stabilizer is one or more of light stabilizer 622, light stabilizer 770, light stabilizer 783 and light stabilizer 944.
7. A mulch film according to any one of claims 1-3 wherein: the antioxidant is one or more of 1076, 1010, 618, DLTP and DSTP; and/or:
the anti-hydrolysis agent is one or more of carbodiimide monomer, N' -bis (2, 6-diisopropylphenyl) carbodiimide, toluene-2, 4-diisocyanate and diphenylmethane diisocyanate; and/or:
the opening agent is one or more of erucamide, oleamide, talcum powder, diatomite and ethylene bis-stearamide.
8. The method for producing a mulching film according to any one of claims 1 to 7, comprising:
optionally, step (1), drying the PBAT resin and the high-crystallinity polylactic acid for 2-6 hours at the temperature of 60-90 ℃; and
fully mixing the PBAT resin, the high-crystallinity polylactic acid, the blocking agent, the chain extender, the UV resistant agent, the light stabilizer, the antioxidant, the hydrolysis resistant agent and the opening agent, extruding and granulating the uniformly mixed materials, and drying the prepared granules;
and (3) adding the dried granules into a film extrusion blow molding machine, and performing extrusion blow molding to obtain the high-barrier full-biodegradable mulch film with fertilizer effect.
9. The method of claim 8, wherein the thickness of the mulch film is 0.006-0.015 mm.
10. The process according to claim 8, wherein in step (2), the granules are extruded in a twin-screw extruder having an aspect ratio of not less than 35 at a temperature in the range of 60 to 180 ℃; drying the granules for 1-3 hours at 60-100 ℃;
in the step (3), the length-diameter ratio of the film extrusion blow molding machine is more than or equal to 25, the condition of the extrusion blow molding process is in the range of 150-190 ℃, and the blowing ratio is controlled to be 1-3: 1.
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| CN108586114A (en) * | 2016-01-12 | 2018-09-28 | 南京林业大学 | A kind of method for preparing fertilizer reducing heavy metal ion content and slow-release function |
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| CN111533604A (en) * | 2020-05-11 | 2020-08-14 | 甘肃放羊娃农业科技有限公司 | Liquid nitrogen fertilizer for improving crop planting and preparation method thereof |
| KR20210005339A (en) * | 2019-07-03 | 2021-01-14 | (주)프렉스 | Biodegradable mulching film having the improved anti-hydrolysis property and manufacturing method thereof |
| CN112812371A (en) * | 2021-01-05 | 2021-05-18 | 湘潭大学 | Nitrogen-phosphorus-containing hydrotalcite-based flame retardant and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108586114A (en) * | 2016-01-12 | 2018-09-28 | 南京林业大学 | A kind of method for preparing fertilizer reducing heavy metal ion content and slow-release function |
| KR20210005339A (en) * | 2019-07-03 | 2021-01-14 | (주)프렉스 | Biodegradable mulching film having the improved anti-hydrolysis property and manufacturing method thereof |
| CN110330773A (en) * | 2019-07-19 | 2019-10-15 | 深圳利琒环保材料有限公司 | A kind of controllable full-biodegradable mulch and preparation method thereof |
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| CN111533604A (en) * | 2020-05-11 | 2020-08-14 | 甘肃放羊娃农业科技有限公司 | Liquid nitrogen fertilizer for improving crop planting and preparation method thereof |
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