CN115044175A - Degradable master batch, preparation method thereof and mulching film containing degradable master batch - Google Patents

Degradable master batch, preparation method thereof and mulching film containing degradable master batch Download PDF

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CN115044175A
CN115044175A CN202110249646.3A CN202110249646A CN115044175A CN 115044175 A CN115044175 A CN 115044175A CN 202110249646 A CN202110249646 A CN 202110249646A CN 115044175 A CN115044175 A CN 115044175A
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master batch
agent
degradation
mulching film
temperature compensation
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刘家磊
何文清
刘琪
李波
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • 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
    • 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
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3036—Sulfides of zinc
    • 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
    • C08K5/00—Use of organic ingredients
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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

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Abstract

The embodiment of the application provides a degradation master batch, a preparation method thereof and a mulching film containing the degradation master batch, wherein the degradation master batch converts ultraviolet light and visible light in sunlight into heat required by soil temperature rise through selection of a temperature compensation agent, so that a temperature compensation effect on the full-biodegradable mulching film is realized. The preparation method of the degradation master batch is simple and feasible, and can be applied to industrial production in a large scale. The temperature compensation full-biodegradable mulching film manufactured by using the temperature compensation degradable master batch fully exerts the strong temperature compensation performance of the degradable master batch and can effectively improve the heat insulation performance of the full-biodegradable mulching film.

Description

Degradation master batch, preparation method thereof and mulching film containing degradation master batch
Technical Field
The application relates to the technical field of biodegradable materials, in particular to a degradable master batch, a preparation method thereof and a mulching film containing the degradable master batch.
Background
In agricultural production, the mulching film has the effects of keeping soil temperature, reducing water evaporation and controlling weeds, and makes contributions to both production and income increase and safe supply of crops. The improvement of the heat preservation performance of the mulching film can not only improve the germination rate of seeds and promote the better growth of crop roots, but also effectively improve the utilization efficiency of nutrients and water in soil, and finally achieve the purpose of improving the growth quality and yield of crops.
However, the use of the traditional polyolefin mulching film causes a serious 'white pollution' problem, the mulching film is not easy to degrade under natural conditions, and residual mulching film in soil can influence the nutrient absorption of crops and the root extension, so that the crop yield is reduced, and the operation of agricultural implements is inconvenient. To solve the problem of "white contamination", biodegradable films have been proposed. However, most of biodegradable mulching films are made of polyester polymer materials, which have large intermolecular gaps and poor barrier property and thermal insulation property compared with traditional polyolefin materials. Therefore, developing a warming measure suitable for the fully biodegradable mulching film becomes a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The embodiment of the application aims to provide a degradable master batch, a preparation method thereof and a mulching film containing the degradable master batch, and is used for improving the heat insulation performance of a full-biodegradable mulching film. The specific technical scheme is as follows:
the present application provides in a first aspect a degradation masterbatch, which comprises: the biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid are mixed according to the mass percentage of 10-90% based on the total mass of the degradable master batch: (2-80%): (0.5-10%): (0.5-20%).
In some embodiments of the present application, the fully biodegradable resin comprises at least one of polybutylene adipate/terephthalate, polybutylene succinate, polylactic acid, or polycaprolactone.
In some embodiments of the present application, the temperature compensating agent comprises at least one of a rare earth oxide light conversion agent, a rare earth organic complex light conversion agent, or an organic conjugated small molecule light conversion agent.
In some embodiments of the present application, the temperature compensating agent comprises Eu (TTA) 3 Phen、[Eu(TTA) 2 Phen(β-T)]And the light conversion agent BDR-15, ZnS and at least one of Mn quantum dots or s-triazine.
In some embodiments herein, the coupling agent comprises a silane-based coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, or a phosphate-based coupling agent.
In some embodiments of the present application, the coupling agent comprises gamma-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, isopropyltris (dioctylphosphato) titanate, isopropyldioleato (dioctylphosphato) titanate or distearoyloxyisopropylaluminate.
In some embodiments of the present application, the processing aid comprises at least one of an antioxidant, an anti-uv agent, a hydrophobic agent, an antimicrobial agent, a lubricant, a dispersant, or a light stabilizer.
In some embodiments herein, the antioxidant comprises at least one of antioxidant 1010, antioxidant 168, antioxidant 264, antioxidant 1076, antioxidant B215, antioxidant B225; the anti-ultraviolet agent comprises at least one of UV531, UV234, UV326, UV327, UV328, UV329 and UV 1130; the hydrophobic agent comprises fatty acid metal soap, paraffin, polyolefin, organic silicon resin or fluorocarbon polymer; the antibacterial agent comprises zirconium phosphate, zeolite, ceramic or activated carbon; the lubricant comprises at least one of polyethylene wax, liquid paraffin, salad oil or stearic acid monoglyceride; the dispersant comprises at least one of EBS or erucamide; the light stabilizer includes at least one of a light stabilizer 770, a light stabilizer 944, a light stabilizer 622, a light stabilizer 2002, a light stabilizer 783, and a light stabilizer 2020.
The second aspect of the present application provides a method for preparing the degradation masterbatch provided by the present application, which includes the following steps:
(1) placing the full-biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid into a reaction kettle, and mixing for 10-30 minutes at normal temperature to obtain a degradation master batch premix;
based on the total mass of the degradation master batch, the mass percentages of the full-biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid are (10-90%): (2-80%): (0.5-10%): (0.5-20%);
(2) and (2) extruding and granulating the premix of the degradation master batch prepared in the step (1) at the temperature of 100-200 ℃ by an extruder to obtain the degradation master batch.
In a third aspect, the present application provides a mulching film, which comprises the degradable masterbatch provided in the present application and a fully biodegradable resin.
In some embodiments of the present application, the mass ratio of the degradation master batch to the fully biodegradable resin is 1 (0.5-199), and the mass percentage content of the temperature compensation agent in the mulching film is 0.05-3%.
According to the degradable master batch, the preparation method thereof and the mulching film containing the degradable master batch, the degradable master batch converts ultraviolet light and visible light in sunlight into heat required by soil temperature rise through selection of the temperature compensation agent, so that the temperature compensation effect on the full-biodegradable mulching film is realized. The preparation method of the degradation master batch is simple and feasible, and can be applied to industrial production in a large scale. The temperature compensation full-biodegradable mulching film manufactured by using the temperature compensation degradable master batch fully exerts the strong temperature compensation performance of the degradable master batch and can effectively improve the heat insulation performance of the full-biodegradable mulching film.
Of course, it is not necessary for any product or method of the present application to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments that can be derived from the disclosure by a person skilled in the art are intended to be within the scope of the disclosure.
The present application provides in a first aspect a degradation masterbatch, which comprises: the degradable master batch comprises the following components in percentage by mass (10-90%) based on the total mass of the degradable master batch: (2-80%): (0.5-10%): (0.5-20%).
In some embodiments of the present application, the all-biodegradable resin may include at least one of polybutylene adipate/terephthalate (PBAT), polybutylene succinate (PBS), polylactic acid (PLA), or Polycaprolactone (PCL), and the like.
In some embodiments of the present application, the temperature compensation agent may include at least one of a rare earth oxide light conversion agent, a rare earth organic complex light conversion agent, or an organic conjugated small molecule light conversion agent, among others. Preferably, the temperature compensation agent comprises Eu (TTA) 3 Phen、[Eu(TTA) 2 Phen(β-T)]At least one of light conversion agent BDR-15 (manufacturer: Guangdong Ke Rui New Material Co., Ltd.), ZnS: Mn quantum dots (manufacturer: Suzhou Xingshi nanometer technology Co., Ltd.), s-triazine, and the like.
Wherein, the application is to Eu (TTA) 3 Synthesis of Phen is not peculiarBut not limited thereto, as long as the object of the present application can be achieved. For example, according to SHARAMA (2015) 586-587 The preparation method comprises the following steps: first, 0.5mM EuCl was added to a beaker (50ml) 3 ·6H 2 O was dissolved in 20ml of deionized water and heated to 60 ℃ on a magnetic stirrer. Second, to 5mM EuCl 3 To the solution were added 1.5mM TTA (5-methylbenzotriazole) and 0.5mM Phen. H in this order 2 Ethanol solution of O. Finally, the mixed solution was stirred uniformly for 1h at 60 ℃ to ensure completion of the reaction. After stirring, filtering, washing the obtained precipitate with deionized water and absolute ethyl alcohol, and vacuum drying at 60 ℃ for 12h to obtain light pink powder-light conversion agent Eu (TTA) 3 Phen(LCA-C)。 1 H NMR(600MHz,DMSO-d6)δ9.11(s,2H),8.51(s,2H), 8.01(s,2H),7.79(s,2H),7.45(s,3H),6.52(s,3H),3.78(s,3H).
This application is to [ Eu (TTA) 2 Phen(β-T)]The synthesis of (b) is not particularly limited as long as the object of the present application can be achieved. For example, it can be obtained according to the following preparation method: 0.5mM EuCl in a beaker (50ml) 3 ·6H 2 O was dissolved in 20ml of deionized water and heated to 60 ℃ on a magnetic stirrer. In sequence to EuCl 3 To the solution was added 1mM TTA, 0.5mM β -T, 0.5mM ethanol solution. Thereafter, the mixed solution was stirred uniformly at 60 ℃ for 1h to ensure completion of the reaction. After stirring, filtering, washing with deionized water and absolute ethyl alcohol, filtering, precipitating, and vacuum drying at 60 deg.C for 12 hr to obtain light yellow powder-light conversion agent [ Eu (TTA) 2 Phen(β-T)](LCA-D)。 1 H NMR(600MHz,DMSO-d6)δ9.12(s,2H),8.51(s,2H), 7.91(d,J＝132.5Hz,4H),7.61–7.27(m,4H),7.23–6.84(m,1H),6.69–6.17(m,7H),3.79(s,2H), 1.73–0.65(m,4H),-0.43(s,2H).
Eu (TTA) mentioned above 3 Phen、[Eu(TTA) 2 Phen(β-T)]The molecular structure with the ligand is as follows:
Figure BDA0002965463000000041
in some embodiments of the present application, there is no particular limitation on the kind of the coupling agent as long as the object of the present application can be achieved. For example, a silane-based coupling agent, a titanic acid-based coupling agent, an aluminate-based coupling agent, a phosphate-based coupling agent, or the like may be included. Preferably, the coupling agent includes gamma-aminopropyltriethoxysilane (KH-550), aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, isopropyltris (dioctylphosphato) titanate, isopropyldioleato (dioctylphosphato) titanate or distearoyloxyisopropylaluminate, and the like.
In some embodiments of the present application, the kind of the processing aid is not particularly limited as long as the object of the present application can be achieved. For example, at least one of an antioxidant, an ultraviolet screening agent, a hydrophobic agent, an antibacterial agent, a lubricant, a dispersant, a light stabilizer, or the like may be included.
The antioxidant may include an antioxidant 1010 (Chinese name: tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, manufacturer: Guangzhou Dalyin New materials Co., Ltd.), an antioxidant 168 (Chinese name: tris [2, 4-di-t-butylphenyl ] phosphite, manufacturer: Beijing Dilong chemical Co., Ltd.), an antioxidant 264 (Chinese name: dibutylhydroxytoluene, manufacturer: Xuzhou Yuanjiangjinghi Engineers Co., Ltd.), an antioxidant 1076 (Chinese name: 2, 4-dimethyl-6- (1-methylpentadecyl) -phenol, manufacturer: Beijing Dilong chemical Co., Ltd.), an antioxidant B215 (manufacturer: Beijing Dilong chemical Co., Ltd.), an antioxidant B225 (Chinese name: phosphorous acid tris (2, 4-di-tert-butylphenyl) ester, manufacturer: beijing delong chemical limited) and the like;
the anti-ultraviolet agent may include UV531 (Chinese name: 2-hydroxy-4-n-octyloxybenzophenone, manufacturer: Wuhankemike biomedical technologies, Ltd.), UV234 (Chinese name: 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, manufacturer: Weibo technologies, Guangzhou), UV326 (Chinese name: 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, manufacturer: Beijing carbofuran technologies, Ltd.), UV327 (Chinese name: 2- (2-hydroxy-3, 5-dibutylphenyl) -5-chlorobenzotriazole, the manufacturer: suzuki chemical research institute, tianjin), UV328 (chinese name: 2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylpropylphenyl) ] -2H-benzotriazole, manufacturer: jiidejia new materials science and technology ltd, Qingdao), UV329 (chinese name: 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, manufacturer: beijing largeway technologies ltd), UV1130 (chinese name: 3- (3- (2-H-benzotriazol-2-yl) -4-hydroxy-5-tert-butylphenyl) -propionic acid-polyethylene glycol 300 ester, manufacturer: shanghai yu chemical limited) and the like;
the hydrophobic agent may include fatty acid metal soaps, paraffins, polyolefins, silicone resins, or fluorocarbon polymers;
the antimicrobial agent may include zirconium phosphate, zeolite, ceramic, or activated carbon;
the lubricant may include at least one of Polyethylene (PE) wax, liquid paraffin, salad oil, or stearic acid monoglyceride, etc.; the dispersant may include at least one of Ethylene Bis Stearamide (EBS), erucamide, or the like;
the light stabilizer may include a light stabilizer 770 (Chinese name: bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, manufacturer: Shanghai Maxim Biochemical technology Co., Ltd.), a light stabilizer 944 (Chinese name: poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amino ] -s-triazine-2, 4-diyl ] - [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] -1, 6-hexanediyl- [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ], manufacturer: Shanghai Maxim Biochemical technology Co., Ltd.), a light stabilizer 622 (Chinese name: succinic acid and 4-hydroxy-2, 2, polymer of 6, 6-tetramethyl-1-piperidinol, manufacturer: jiidejia new material science and technology ltd, Qingdao), a light stabilizer 2002 (chinese name: bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) nickel, manufacturer: shayanqinjiang chemical limited), a light stabilizer 783 (chinese name: complex of poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4-bis [ (2,2,6, 6-tetramethyl-piperidyl) imino ] -1, 6-hexadiene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] } with polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol) ester, manufacturer: filial profound chemical limited), photostabilizer 2020 (chinese name: 1, 6-hexanediamine, manufacturer: shanghai Michelin Biochemical technologies, Inc.), and the like.
The application provides a degradation master batch, through the addition of temperature compensation agent to and the reasonable collocation of mass percent between temperature compensation agent and full biodegradable resin, coupling agent, the processing auxiliary agent, ultraviolet ray, the visible light in the sunlight convert the required heat of soil intensification, in order to realize the temperature compensation effect to full biodegradable plastic film. The degradation master batch is used in the full-biodegradable mulching film, so that the strong temperature compensation performance of the degradation master batch can be fully exerted, and the heat preservation performance of the full-biodegradable mulching film is effectively improved.
The second aspect of the present application provides a method for preparing the degradation masterbatch provided by the present application, which includes the following steps:
(1) placing the full-biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid into a reaction kettle, and mixing for 10-30 minutes at normal temperature to obtain a degradation master batch premix;
based on the total mass of the degradation master batch, the mass percentages of the full-biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid are (10-90%): (2-80%): (0.5-10%): (0.5-20%);
(2) and (2) extruding and granulating the premix of the degradation master batch prepared in the step (1) at the temperature of 100-200 ℃ by an extruder to obtain the degradation master batch.
In the present application, the kind of the extruder is not particularly limited as long as the object of the present application can be achieved. For example, one of a twin screw extruder or a single screw extruder, etc. may be included.
The method for preparing the degradation master batch has the advantages of easily available production raw materials and simple operation, can be widely applied to industrial production, and has great significance for large-area popularization of the full-biodegradable mulching film.
In a third aspect, the present application provides a mulching film, which comprises the degradable masterbatch provided in the present application and the fully biodegradable resin provided in the present application.
In some embodiments of the present application, the mass ratio of the degradation master batch to the fully biodegradable resin is 1 (0.5-199), and the mass percentage content of the temperature compensation agent in the mulching film is 0.05-3%. The mass ratio of the degradable master batches to the fully biodegradable resin is controlled within the range, so that the content of the temperature compensation agent in the mulching film reaches the optimal range, the temperature compensation agent in the mulching film fully exerts the strong temperature compensation performance, and the heat insulation performance of the fully biodegradable mulching film is effectively improved.
In the present application, there is no particular limitation on the preparation method of the mulching film provided herein, as long as the object of the present application can be achieved. For example, the following preparation method can be employed: mixing the degradable master batch and the full-biodegradable resin in a reaction kettle according to the mass ratio of 1 (0.5-199) to obtain a mulching film premix; and (3) performing film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperatures of a feeding section, a melting and blending section and an extrusion section of the film blowing machine at 130 ℃, 160 ℃ and 200 ℃, respectively, controlling the rotating speed of a host at 750-.
In the present application, the kind of the film blowing machine is not particularly limited as long as the object of the present application can be achieved. For example, the mold may include one of DX-C75 type, DX-C90 type, DX-C105 type or DX-C120 type, and the like, wherein the manufacturers of DX-C75 type, DX-C90 type, DX-C105 type and DX-C120 type are Thailand machinery, Inc. of Ruian.
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
The test method and the test equipment are as follows:
and (3) testing the thickness of the mulching film:
the measurements were carried out using a Millimar C1200 compact length measuring instrument from the company Mahr GmbH.
Testing 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 50mm, a narrow parallel width of 10mm, a drawing speed of 500mm/min and a room temperature of 25 ℃.
Example 1
< preparation of mother pellets for degradation >
Placing the fully biodegradable resin PBAT, the temperature compensator BDR-15, the coupling agent KH550, the processing aid EBS and the light stabilizer 783 into a reaction kettle according to the mass ratio of 66.7:7.4:7.4:3.7:14.8, and mixing for 20 minutes at normal temperature to obtain a degrading master batch premix;
and extruding and granulating the prepared degradation master batch premix at 150 ℃ by a single-screw extruder to obtain the degradation master batch.
< preparation of mulching film >
Mixing the prepared degradation master batch and full-biodegradable resin PBAT in a reaction kettle according to the mass ratio of 1:9 to obtain a mulching film premix;
and (3) carrying out film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperatures of a feeding section, a melt blending section and an extrusion section of the film blowing machine to be 120 ℃, 150 ℃ and 180 ℃, respectively, controlling the rotating speed of a main machine to be 1000r/min and the traction speed to be 2m/min, and obtaining the temperature compensation degradable mulching film with the thickness of 10 mu m, wherein the mass percentage of the temperature compensation agent in the mulching film is 1%.
Example 2
< preparation of masterbatch degradation >
Fully biodegradable resin PBAT and PLA, a temperature compensation agent Eu (TTA) 3 Phen, a coupling agent KH550, a processing aid EBS and a light stabilizer 783 are placed in a reaction kettle according to the mass ratio of 60.3:17.2:8.6:8.6:4.3:1, and the reaction kettle is at normal temperatureMixing for 20 minutes to obtain a degradation master batch premix;
and extruding and granulating the prepared degradation master batch premix at 150 ℃ by a single-screw extruder to obtain the degradation master batch.
< preparation of mulching film >
Mixing the prepared degradation master batch and full-biodegradable resin PBAT in a reaction kettle according to the mass ratio of 2:8 to obtain a mulching film premix;
and (3) carrying out film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperatures of a feeding section, a melt blending section and an extrusion section of the film blowing machine to be 120 ℃, 150 ℃ and 180 ℃, respectively, controlling the rotating speed of a main machine to be 1000r/min and the traction speed to be 2m/min, and obtaining the temperature compensation degradable mulching film with the thickness of 10 mu m, wherein the mass percentage of the temperature compensation agent in the mulching film is 2%.
Example 3
< preparation of mother pellets for degradation >
Mixing fully biodegradable resin PBAT, PBS and temperature compensation agent [ Eu (TTA ] 2 Phen(β-T)]And ZnS, Mn quantum dots, a coupling agent KH550, a processing aid EBS and a light stabilizer 783 are placed in a reaction kettle according to the mass ratio of 57.9:16.5:4.1:8.3:8.3:0.8:4.1, and mixed for 20 minutes at normal temperature to obtain a degradation master batch premix;
and extruding and granulating the prepared degradation master batch premix at 150 ℃ by using a single-screw extruder to obtain the degradation master batch.
< preparation of mulching film >
Mixing the prepared degradation master batch and full-biodegradable resin PBAT in a reaction kettle according to the mass ratio of 3:7 to obtain a mulching film premix;
and (3) carrying out film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperatures of a feeding section, a melt blending section and an extrusion section of the film blowing machine to be 120 ℃, 150 ℃ and 180 ℃, respectively, controlling the rotating speed of a main machine to be 1000r/min and the traction speed to be 2m/min, and thus obtaining the temperature compensation degradable mulching film with the thickness of 10 microns, wherein the mass percentage of the temperature compensation agent in the mulching film is 3%.
Example 4
< preparation of mother pellets for degradation >
Placing the fully biodegradable resin PBAT and PCL, the temperature compensation agent sym-triazine, the coupling agent KH550, the processing aid EBS and the light stabilizer 783 into a reaction kettle according to the mass ratio of 59.3:7.4:7.4:7.4:14.8:3.7, and mixing for 20 minutes at normal temperature to obtain a degradation master batch premix;
and extruding and granulating the prepared degradation master batch premix at 150 ℃ by a single-screw extruder to obtain the degradation master batch.
< preparation of mulching film >
Mixing the prepared degradable master batch, the fully biodegradable resin PBAT and the PLA in a reaction kettle according to the mass ratio of 0.5:6:3.5 to obtain a mulching film premix;
and (3) carrying out film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperature of a feeding section, a melting and blending section and an extrusion section of the film blowing machine to be 120 ℃, 150 ℃ and 180 ℃, respectively, controlling the rotating speed of a main machine to be 1000r/min and the traction speed to be 2m/min, and obtaining the temperature compensation degradable mulching film with the thickness of 10 mu m, wherein the mass percentage of the temperature compensation agent in the mulching film is 0.5%.
Example 5
< preparation of master batch > was the same as in example 2.
< preparation of mulching film >
Mixing the prepared degradation master batch, the fully biodegradable resin PBAT and the PBS in a reaction kettle according to the mass ratio of 0.1:6:3.9 to obtain a mulching film premix;
and (3) carrying out film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperatures of a feeding section, a melt blending section and an extrusion section of the film blowing machine to be 120 ℃, 150 ℃ and 180 ℃, respectively, controlling the rotating speed of a main machine to be 1000r/min and the traction speed to be 2m/min, and obtaining the temperature compensation degradable mulching film with the thickness of 10 mu m, wherein the mass percentage of the temperature compensation agent in the mulching film is 0.1%.
Example 6
< preparation of degranulation mother pellets > the same as in example 2.
< preparation of mulching film >
Mixing the prepared degradation master batch, the fully biodegradable resin PBAT and the PCL in a reaction kettle according to the mass ratio of 0.05:6:3.95 to obtain a mulching film premix;
and (3) carrying out film blowing molding processing on the mulching film premix by using a film blowing machine, controlling the temperature of a feeding section, a melting and blending section and an extrusion section of the film blowing machine to be 120 ℃, 150 ℃ and 180 ℃, respectively, controlling the rotating speed of a main machine to be 1000r/min and the traction speed to be 2m/min, and obtaining the temperature compensation degradable mulching film with the thickness of 10 mu m, wherein the mass percentage of the temperature compensation agent in the mulching film is 0.05%.
Example 7
< preparation of mother pellets for degradation >
Mixing fully biodegradable resin PBAT and temperature compensation agent Eu (TTA) 3 Placing Phen, a coupling agent KH550, a processing aid EBS and a light stabilizer 783 into a reaction kettle according to the mass ratio of 80:9:1:0.8:0.2, and mixing for 20 minutes at normal temperature to obtain a master batch premix;
and extruding and granulating the prepared degradation master batch premix at 150 ℃ by using an extruder to obtain the degradation master batch.
< preparation of mulching film > was the same as in example 1.
Example 8
< preparation of mother pellets for degradation >
Mixing fully biodegradable resin PBAT, PLA, PBS and PCL, temperature compensation agent Eu (TTA) 3 Placing Phen, a coupling agent KH550, a processing aid EBS and a light stabilizer 783 into a reaction kettle according to the mass ratio of 90:2:0.5:6.3:1.2, and mixing for 20 minutes at normal temperature to obtain a degradation master batch premix;
and extruding and granulating the prepared degradation master batch premix at 150 ℃ by using an extruder to obtain the degradation master batch.
< preparation of mulching film > was the same as in example 1.
Comparative example 1
< preparation of mulching film >
And (3) carrying out film blowing molding processing on the fully biodegradable resin PBAT by using a film blowing machine, and respectively controlling the temperature of a feeding section, a melt blending section and an extrusion section of the film blowing machine at 120 ℃, 150 ℃ and 180 ℃, controlling the rotating speed of a main machine at 1000r/min and the traction speed at 2m/min to obtain the mulching film with the thickness of 10 mu m.
The data and test results for examples 1-8, comparative example 1 are detailed in Table 1.
Figure BDA0002965463000000121
Note: the "/" in table 1 indicates no corresponding preparation parameters.
It can be seen from comparison between examples 1-8 and the comparative example that the application of the degradation master batch provided by the application to the full-biodegradable mulching film can improve the tensile strength and the elongation at break of the full-biodegradable mulching film, can fully exert the strong temperature compensation performance of the degradation master batch, and effectively improve the heat insulation performance of the full-biodegradable mulching film.
In general, the application provides a degradation master batch, a preparation method thereof and a mulching film containing the degradation master batch, wherein the degradation master batch can convert ultraviolet light and visible light in sunlight into heat required by soil temperature rise through adding a temperature compensation agent and reasonably matching the temperature compensation agent with full-biodegradable resin, a coupling agent and a processing aid in percentage by mass, so that a temperature compensation effect on the full-biodegradable mulching film is realized, and the method has great significance for large-area popularization of the full-biodegradable mulching film. The preparation method of the degradation master batch provided by the application has the advantages of easily available production raw materials and simplicity in operation, and can be widely applied to industrial production. The degradation master batch is used in the full-biodegradable mulching film, so that the strong temperature compensation performance of the degradation master batch can be fully exerted, and the temperature compensation full-biodegradable mulching film with excellent thermal insulation performance is obtained.
The above description is only for the preferred embodiment of the present application, and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (11)

1. A degradation masterbatch, comprising: the biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid are mixed according to the mass percentage of 10-90% based on the total mass of the degradable master batch: (2-80%): (0.5-10%): (0.5-20%).
2. The degradation masterbatch of claim 1, wherein the fully biodegradable resin comprises at least one of polybutylene adipate/terephthalate, polybutylene succinate, polylactic acid, or polycaprolactone.
3. The degradation masterbatch of claim 1, wherein the temperature compensator comprises at least one of a rare earth oxide light conversion agent, a rare earth organic complex light conversion agent, or an organic conjugated small molecule light conversion agent.
4. The degrading mother particle of claim 3, wherein the temperature compensating agent comprises Eu (TTA) 3 Phen、[Eu(TTA) 2 Phen(β-T)]And the light conversion agent BDR-15, ZnS and at least one of Mn quantum dots or s-triazine.
5. The degradation masterbatch of claim 1, wherein the coupling agent comprises a silane-based coupling agent, a titanic acid-based coupling agent, an aluminate-based coupling agent, or a phosphate-based coupling agent.
6. The degradation masterbatch of claim 5, wherein the coupling agent comprises gamma-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, isopropyl tris (dioctylphosphatoxy) titanate, isopropyl bis (dioctylphosphatoxy) titanate, or distearoyloxyisopropyl aluminate.
7. The degranulation masterbatch of claim 1, wherein the processing aid comprises at least one of an antioxidant, an anti-ultraviolet agent, a hydrophobic agent, an antimicrobial agent, a lubricant, a dispersant, or a light stabilizer.
8. The degradation masterbatch of claim 7, wherein the antioxidant comprises at least one of antioxidant 1010, antioxidant 168, antioxidant 264, antioxidant 1076, antioxidant B215, and antioxidant B225;
the anti-ultraviolet agent comprises at least one of UV531, UV234, UV326, UV327, UV328, UV329 and UV 1130;
the hydrophobic agent comprises fatty acid metal soap, paraffin, polyolefin, organic silicon resin or fluorocarbon polymer;
the antibacterial agent comprises zirconium phosphate, zeolite, ceramic or activated carbon;
the lubricant comprises at least one of polyethylene wax, liquid paraffin, salad oil or stearic acid monoglyceride;
the dispersant comprises at least one of EBS or erucamide;
the light stabilizer includes at least one of a light stabilizer 770, a light stabilizer 944, a light stabilizer 622, a light stabilizer 2002, a light stabilizer 783, and a light stabilizer 2020.
9. A method of making the degradation masterbatch of any one of claims 1 to 8, comprising the steps of:
(1) placing the full-biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid in a reaction kettle, and mixing for 10-30 minutes at normal temperature to obtain a degradation master batch premix;
based on the total mass of the degradation master batch, the mass percentages of the full-biodegradable resin, the temperature compensation agent, the coupling agent and the processing aid are (10-90%): (2-80%): (0.5-10%): (0.5-20%);
(2) and (2) extruding and granulating the degradation master batch premix prepared in the step (1) at the temperature of 100-200 ℃ by an extruder to obtain the degradation master batch.
10. A mulching film comprising the degradation mother particle as set forth in any one of claims 1 to 9 and a fully biodegradable resin.
11. The mulching film according to claim 10, wherein the mass ratio of the degradation master batch to the full-biodegradable resin is 1 (0.5-199), and the mass percentage of the temperature compensation agent in the mulching film is 0.05-3%.
CN202110249646.3A 2021-03-08 2021-03-08 Degradable master batch, preparation method thereof and mulching film containing degradable master batch Pending CN115044175A (en)

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CN106279924A (en) * 2016-08-30 2017-01-04 佛山安亿纳米材料有限公司 A kind of sulfur indium compound system quantum dot light conversion film and preparation method thereof
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